CN103524697B - A kind of polyurethane-urea hydrogel and preparation method thereof - Google Patents
A kind of polyurethane-urea hydrogel and preparation method thereof Download PDFInfo
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- 0 *C1=CC(*)=C(C[Cl+])CC1 Chemical compound *C1=CC(*)=C(C[Cl+])CC1 0.000 description 6
- KVOZXXSUSRZIKD-UHFFFAOYSA-N C=CCC1CCCCC1 Chemical compound C=CCC1CCCCC1 KVOZXXSUSRZIKD-UHFFFAOYSA-N 0.000 description 1
- VBHBLOUILJNZKN-UHFFFAOYSA-N CC([O](c1cccc(C#N)c1)#C)=O Chemical compound CC([O](c1cccc(C#N)c1)#C)=O VBHBLOUILJNZKN-UHFFFAOYSA-N 0.000 description 1
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- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The present invention relates to a kind of polyurethane-urea hydrogel and preparation method thereof.Comprise two kinds of preparation methods, one is add vulcabond and catalyst reaction in polyoxyethylene glycol (PEG) organic solution, then adds chainextender diamines, and precipitation obtains product in organic solvent; Wherein, the mol ratio of PEG ︰ bis-Yi Qing Suan Zhi ︰ diamines is 1: 2 ︰ 1.Two is add N in PEG organic solution, N '-dicarbapentaborane diimidazole reaction, then adds excessive chainextender diamines, must arrive the macromole that two ends are amidos, finally add vulcabond again, precipitation obtains product in organic solvent, wherein, the mol ratio of PEG ︰ vulcabond is 1: 2.Polyurethane-urea hydrogel provided by the invention has the advantages that elongation is large, tensile strength is high, and there is shape memory function, in biology device that bio-medical hydrogel, organizational project, hydrogel scaffold material and shape memory function are given etc., there is application prospect.
Description
Technical field
The present invention relates to biological medical polymer material and supramolecular chemistry field, particularly relate to and a kind of there is excellent mechanical property and the polyurethane-urea hydrogel that can realize water or thermo-responsive shape memory function and preparation method thereof.
Background technology
Hydrogel is a kind of swelling in water, but the material that can not dissolve.In the past few decades, have a large amount of work to be devoted to the research of hydrogel, this material of hydrogel can be widely used in biomedical aspect, such as, and the replacement of pharmaceutical carrier, wound dressing, cartilage, artificial kidney film and other medical devices.But due to hydrogel be in swollen state time, be usually expressed as weak mechanical property, so its application is limited by very large.Because as bio-medical material, except need having certain biological similarities and consistency, also need to have the deformation restorability under excellent physical strength, stability and External Force Acting.The method of traditional raising hydrogel mechanical property mainly depends on the density improving chemically crosslinked point, but raising cross-linking set can cause the reduction of water-intake rate usually, and the process removing unreacted linking agent is very loaded down with trivial details.Due to these restrictions above, the hydrogel of physical crosslinking starts to be paid close attention to widely.Document (Macromolecules, 2010,43,7637 – 7649) report a kind of hydrogel, soft section of hydrophilic polyoxyethylene glycol (PEG) is combined with the hard section of hydrophobic POSS, the two can form crystallizing field, physical crosslinking point can be served as in hard section crystallizing field, thus forms organic-inorganic combined network, and its shearing modulus reaches as high as 4.0MPa, but because it is composite organic-inorganic material, therefore Shortcomings in the consistency of material.
Containing carbamate groups and urea groups in polyurethane-urea hydrogel, intermolecularly can form a large amount of hydrogen bonds, these Hyarogen-bondings are equivalent to the cross-linking set of transient state one by one, thus are conducive to the enhancing of the intensity of the hydrogel synthesized.But owing to containing a large amount of water moleculess in hydrogel, in the process forming hydrogen bond, water can be competed with the hydrogen bond of polyurethane-urea self, to such an extent as to the hydrogen bond reduced number in hydrogel self structure, so the polyurethane-urea hydrogel intensity of great majority synthesis is very low.Document (Biomacromolecules, 2012,13,3966 3976) a kind of injectable PEG-urea block copolymer hydrogel very stable in water relying on the synergy between multiple hydrogen bonding and hydrophobic forces to be formed is reported, by the density of adjustment physics cross-linking set and the length of hydrophobic segment, its modulus can regulate between 0.4 ~ 20kPa.But because the hydrophobic aggregation effect formed in molecule is not very strong, from form, this hydrogel is still rarer glutinous, is difficult to sizing, much needs thus being restricted of the application aspect of high mechanical strength.
In addition, need the bio-medical material of implant into body in use, how to make the wound that causes patient in implantation process minimum, how to take out after implantation, also receive increasing concern.The artificial device of shape-memory polymer (SMPs) type meets the demand of this respect just.This is because, there are the SMPs goods of certain original shape, required deformation can be produced under specific work program, be prepared into the temporary shapes of applicable Minimally Invasive Surgery, after this temporary shapes implants, its original shape can be returned under external stimulus (as hot, optical, electrical, magnetic and solvent etc.).But the deformation of current all SMPs (comprising currently reported water-responsive SMPs) produces and all needs at a higher temperature (the T of polymkeric substance
gor T
mcarry out above), easily cause the activity of the bioactive ingredients of material surface or inside (as albumen and medicine etc.) greatly to reduce, even lost efficacy.Meanwhile, the SMPs of the overwhelming majority is thermosensitive type at present, and its deformation recovers also to need to carry out at a higher temperature, easily causes damage to the tissue around implant site.Publication number is the hydrogel that the PCT of WO2012/168392A1 patent reports the shape memory of a kind of water and hot double-response function, the hydrogel of dry state is characterized in be heated to 70 DEG C, it is made to change elastomeric state into, and then a temporal profile is designed under elastomeric state, temperature drops to after below transition temperature, this temporary shapes is fixed, and then under the stimulation of water or heat, to return to original shape.
Summary of the invention
Problem to be solved by this invention overcomes the more weak deficiency of physical strength that synthesis of polyurethane urea hydrogel in prior art exists, there is provided a kind of synthetic method simple, physical strength is high, applied widely, and there is the shape memory function of temperature and water-responsive simultaneously, polyurethane-urea hydrogel of high comprehensive performance and preparation method thereof.
Realize the synthetic method that object technical scheme of the present invention is to provide a kind of polyurethane-urea hydrogel, described hydrogel is the multipolymer of polyoxyethylene glycol, vulcabond and diamines, and its structural formula is:
, in formula, R is alkyl in vulcabond between two isocyanos or aromatic base, and R ' is the alkyl in diamines between two amidos or aromatic base,
for polyoxyethylene glycol, n is the polymerization degree.
Above-described polyurethane-urea hydrogel, its elongation at break stretched is 200 ~ 2000%; Tensile strength is 10 ~ 2000kPa.
The hydrogel based multiple hydrogen bonding in urea groups of polyurethane-urea provided by the invention and the synergistic method of hydrophobic aggregation strengthen the intensity of polyurethane-urea hydrogel.
The preparation of the polyurethane-urea hydrogel that the present invention relates to, realizes by following two routes:
；
Or
；
In formula, R represents alkyl in vulcabond between two isocyanos or aromatic base, and R ' represents alkyl in diamines between two amidos or aromatic base,
represent polyoxyethylene glycol (PEG), n is the polymerization degree.
The concrete steps of the first preparation method are as follows:
(1) be dissolved in organic solution A by polyoxyethylene glycol, described organic solvent A is the one in DMF, acetone, chloroform, methylene dichloride, ethylene dichloride; Add vulcabond and catalyzer again, described catalyzer is the one in stannous octoate, dibutyl tin laurate, N-ethylmorpholine, N-methylmorpholine, pyridine, N, N '-lutidine; Be react 1 ~ 5 hour under the condition of 20 ~ 80 DEG C in temperature, in molar ratio, Ju Yi bis-Chun ︰ vulcabond is 1 ︰ 2;
(2) adding chainextender diamine monomer, is 20 ~ 80 DEG C in temperature, stirred under nitrogen atmosphere reaction 1 ~ 5 hour, and in molar ratio, Ju Yi bis-Chun ︰ bis-Yi Qing Suan Zhi ︰ diamines is 1 ︰ 2 ︰ 1;
(3) product is placed in organic solvent B after terminating by reaction, and described organic solvent B is the one in normal hexane, normal heptane, isohexane, isoheptane, hexanaphthene, ether, obtains white fluffy solid throw out; Be dissolved in again after drying in organic solvent C, described organic solvent C is the one in methyl alcohol, ethanol, chloroform or methylene dichloride, pours die for molding into, after solvent evaporates is dried, swelling until reach swelling equilibrium in distilled water, obtain a kind of polyurethane-urea hydrogel.
The concrete steps that another kind prepares the method for polyurethane-urea hydrogel are as follows:
(1) be dissolved in organic solution A by polyoxyethylene glycol, described organic solvent A is the one in DMF, acetone, chloroform, methylene dichloride, ethylene dichloride; In molar ratio, add excessive N again, N '-dicarbapentaborane diimidazole, fully react under room temperature, nitrogen protection condition, precipitated in organic solvent B by solution after end, described organic solvent B is the one in normal hexane, normal heptane, isohexane, isoheptane, hexanaphthene, ether; By obtain white powder throw out suction filtration, drying;
(2) product that step (1) obtains is dissolved in organic solution A, in molar ratio, add excessive chainextender diamine monomer, after fully reacting under room temperature, nitrogen protection condition, through centrifugal, filtration, obtain water white transparency clear liquid, be placed in organic solution C and precipitate, described organic solvent C is the one in methyl alcohol, ethanol, chloroform or methylene dichloride, obtains white powdery solid;
(3) be dissolved in organic solution A by the product that step (2) obtains, then add vulcabond, in molar ratio, Ju Yi bis-Chun ︰ vulcabond is 1 ︰ 1,25 ~ 60 DEG C, react under nitrogen protection condition;
(4) product that step (3) obtains is placed in ether to precipitate, obtains white fluffy solid, be dissolved in chloroform after drying, pour die for molding into, after solvent evaporates is dried, swelling until reach swelling equilibrium in distilled water, obtain a kind of polyurethane-urea hydrogel.
The molecular weight of polyoxyethylene glycol described in technical solution of the present invention is 200 ~ 20000g/mol.
Described vulcabond is the vulcabond ONC-(CH of aliphatic chain
2)
4-NCO, ONC-(CH
2)
6-NCO, ONC-(CH
2)
8-NCO, ONC-(CH
2)
12one in-NCO, 1,5-bis-isocyanic acid-2-methylpentane, or be alicyclic vulcabond
,
,
,
in one, or be aromatic vulcabond
,
,
,
,
in one.
Described chainextender diamine monomer is
,
,
,
, H
2n-(CH
2)
4-NH
2, H
2n-(CH
2)
6-NH
2, H
2n-(CH
2)
8-NH
2, H
2n-(CH
2)
10-NH
2in one.
Described chainextender diamine monomer is
,
,
,
, H
2n-(CH
2)
4-NH
2, H
2n-(CH
2)
6-NH
2, H
2n-(CH
2)
8-NH
2, H
2n-(CH
2)
10-NH
2in one.
Owing to implementing technique scheme, compared with prior art, the invention has the advantages that:
1, because the product of synthesis is linear molecule, dissolve in many organic solvents or carry out melt-processed, greatly facilitating its processed and applied.And introduce a large amount of carbamate groups and urea groups, can form multiple hydrogen bonding between them, this intermolecular reactive force effectively can provide the mechanical property of hydrogel.
2, when gel state, hydrogen bond group wraps up by the hydrophobic microcell that the hydrophobic chain self-assembly on urea groups both sides is formed, water segregation in itself and hydrophilic polymer chains and gel network is come, reach the effect strengthening hydrogen bond, these hydrogen bonding interaction enhanced can make again the hydrophobic shell tight clusters more of its periphery, realize the synergistic enhancing effect between hydrogen bond and hydrophobic aggregation reactive force.
3, while the polyurethane-urea hydrogel of the present invention's synthesis has temperature response shape memory function, there is again water-responsive shape memory function under room temperature.Meanwhile, the good tensile property of made hydrogel and PEG crystallization phases adjoint in process is decrystallized in dehydration crystallization-water suction also can be relied on to change realize that the deformation under room temperature, water medium condition produces, fixing and recovery.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the polyurethane-urea hydrogel that the embodiment of the present invention 1 provides;
Fig. 2 is the nuclear magnetic spectrogram of the polyurethane-urea hydrogel that the embodiment of the present invention 1 provides;
Fig. 3 is the stress strain diagrm of the tension test of the polyurethane-urea hydrogel that the embodiment of the present invention 1 provides;
Fig. 4 is the stress strain diagrm of five cyclic tension tests under 300% of the polyurethane-urea hydrogel that the embodiment of the present invention 1 provides;
Fig. 5 is the stress strain diagrm of five cyclic tension tests under 200% of the polyurethane-urea hydrogel that the embodiment of the present invention 1 provides;
Fig. 6 is the stress strain diagrm of five cyclic tension tests under 100% of the polyurethane-urea hydrogel that the embodiment of the present invention 1 provides;
The rheometer test figure of the polyurethane-urea hydrogel that the polyoxyethylene glycol that Fig. 7 is use molecular weight that the embodiment of the present invention 1 provides is 4000g/mol synthesizes;
The rheometer test figure of the polyurethane-urea hydrogel that the polyoxyethylene glycol that Fig. 8 is use molecular weight that the embodiment of the present invention 4 provides is 2000g/mol synthesizes;
Fig. 9 is the DSC test curve figure of polyurethane-urea hydrogel when different moisture content that the embodiment of the present invention 4 provides.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further elaborated.
Embodiment 1
A kind of high-strength polyurethane urea hydrogel that the present embodiment provides, its synthetic route is:
；
In formula, R represents alkyl in vulcabond between two isocyanos or aromatic base, and R ' represents alkyl in diamines between two amidos or aromatic base,
represent polyoxyethylene glycol (PEG), its molecular weight is 200 ~ 20000g/mol; N is the polymerization degree.
The concrete steps of synthesis are: be add vulcabond OCN-(CH in the DMF solution of the PEG of 4000g/mol at molecular weight
2)
12-NCO, then add 5 μ l catalyst dibutyltin dilaurylate, react 2h at 80 DEG C.And then diamines H is added in reaction flask
2n-(CH
2)
6-NH
2, at 20 DEG C, stirred under nitrogen atmosphere reaction 3h.The mol ratio of strict control reaction raw materials, i.e. PEG ︰ bis-Yi Qing Suan Zhi ︰ diamines=1 ︰ 2 ︰ 1.After reaction terminates, the solution that the viscosity obtained is very large is precipitated out in normal hexane, obtains white fluffy solid.Product is carried out moltenly after drying then pour die for molding into in ethanol, after solvent evaporates is dried, be allowed to condition in distilled water swelling until reach swelling equilibrium, just obtain the hydrogel of polyurethane-urea.
See accompanying drawing 1, it is the infrared spectrum of the polyurethane-urea hydrogel that the present embodiment provides; Visible in figure, 2850cm
-1: methylene peak; 1670-1690cm
-1: allophanyl; 1530cm
-1: carbamate eigen vibration peak.
See accompanying drawing 2, it is the nuclear magnetic spectrogram of the polyurethane-urea hydrogel that the present embodiment provides; Test condition is CDCl3, h400,
1h-NMR (400MHz, CDCl
3); Wherein δ=7.26 (solvent peak, CDCl
3); 4.20 (hydrogen on the carbon of carbamate side); 3.79-3.42 (4nH, PEG); 3.20-3.10 (hydrogen on the carbon of urea groups side); 1.90-1.55 (hydrogen on the carbon of carbamate side); 1.40-1.20 (PEG).
The vulcabond of the present embodiment aliphatic chain and the macromole polyurethane-urea hydrogel of diamines synthetic linear, have following structure:
，
In formula, R represents alkyl in vulcabond between two isocyanos or aromatic base, and R ' represents alkyl in diamines between two amidos or aromatic base,
represent polyoxyethylene glycol (PEG), its molecular weight is 200 ~ 20000g/mol; N is the polymerization degree.Containing a large amount of urea groups in this linear long chain molecule, a large amount of hydrogen bonds can be formed between urea groups, hydrogen bond group wraps up by the hydrophobic microcell that the hydrophobic chain self-assembly simultaneously in molecule is formed, water segregation in itself and hydrophilic polymer chains and gel network is come, reach the effect strengthening hydrogen bond, these hydrogen bonding interaction enhanced can make again the hydrophobic shell tight clusters more of its periphery, realize the synergistic enhancing effect between hydrogen bond and hydrophobic aggregation reactive force, therefore, mechanicalness is effectively improved.
See accompanying drawing 3, it is the Elongation test graphic representation of the polyurethane-urea hydrogel that the present embodiment provides, and as can be seen from Figure, its elongation at break is 1320%, and corresponding stress is 2000kPa.Namely, this hydrogel can be moved about 13 times of former length to and just can rupture, and the highest drawing force born is 2000kPa.The scope of its elongation at break of product of the present invention's synthesis can regulate in 200% ~ 2000%, and the character of this high strength is likely applied to the biomaterials such as the replacement of tissue engineering bracket and cartilage.
See accompanying drawing 4, it is the cyclic tension test curve figure of the polyurethane-urea hydrogel that the present embodiment provides, and Fig. 4, Fig. 5, Fig. 6 are respectively five cyclic tension tests under 300%, 200%, 100%.As seen from the figure, 300%, 200% cyclic tension test is in the process of first circulation, sample all there occurs energy waste to a certain degree, when stress is zero, the strain that X-coordinate is corresponding is respectively 20% and 12%, and namely after a cyclic tension, sample can be returned to 80% and 88% of former length respectively.All can not be returned to the position of original stress under circulating in same strain for subsequently four times, but subsequently circulate that difference is little substantially for its stress-strain curve for four times.Be different from above two kinds of curves, in the cyclic tension process of 100%, its recovery is relatively good, does not occur waste of energy circle.This shows, can there is waste of energy to a certain degree in this polyurethane-urea hydrogel when multi-drawing, make it can not be returned to former length, but this dissipation is not very large, interpret sample has good elasticity, and especially when level of stretch is not very large, sample can be returned to former length substantially.
See accompanying drawing 7, it is the rheometer test figure of the polyurethane-urea hydrogel that the present embodiment provides; X-coordinate is circular frequency, and ordinate zou is stress, and two lines are respectively the curve that Young's modulus and loss moduli change with circular frequency.Fig. 7 is the rheological diagram of the polyurethane-urea hydrogel using the polyoxyethylene glycol that molecular weight is 4000g/mol to synthesize.As can be seen from the figure, G ' Young's modulus curve is in G all the time " top of loss moduli curve, illustrate that this hydrogel shows the character of solid, and its Young's modulus is about 45kPa, the strength ratio that also reflects hydrogel is better.
The polyurethane-urea hydrogel that the present embodiment provides has water and thermal response shape memory function.
The shape memory condition of water-responsive is: be designed to original shape by after polyurethane-urea swelling behavior, its swelling rear utilize the stretching-dehydration at room temperature of its snappiness after obtain temporary shapes, after the dry state gel of the temporary shapes after fixing is put into the distilled water water suction under room temperature, its shape returns to original shape, realizes the memory function of shape.
The shape memory condition of thermal response is: be designed to original shape by after polyurethane-urea swelling behavior, after polyurethane-urea hydrogel is heated to 50 DEG C, stretching is carried out to it and obtain temporary shapes, the dry state gel of the temporary shapes after fixing is put into 50 DEG C of silicone oil, its shape returns to original shape, realizes the memory function of shape.
Embodiment 2
The present embodiment provides a kind of synthetic method of high-strength polyurethane urea hydrogel, and concrete steps are as follows:
Be add vulcabond IPDI in the PEG acetone soln of 10000g/mol at molecular weight, then add the sub-tin of 5 μ l octoate catalysts, at 50 DEG C, react 3h.And then in reaction flask, add diamines 3,3 '-methylene dianiline, nitrogen protection stirring reaction 3h at 40 DEG C.The mol ratio of strict control reaction raw materials, i.e. PEG ︰ bis-Yi Qing Suan Zhi ︰ diamines=1 ︰ 2 ︰ 1.After reaction terminates, the solution that the viscosity obtained is very large is precipitated out in ether, obtains white fluffy solid.Product is carried out moltenly after drying then pour die for molding into in chloroform, after solvent evaporates is dried, be allowed to condition in distilled water swelling until reach swelling equilibrium, just obtain the hydrogel of polyurethane-urea.
The feature of the present embodiment uses the PEG that alicyclic vulcabond IPDI and molecular weight are 6000g/mol to react, and then be with the aromatic diamine synthesis of polyurethane urea hydrogel of phenyl ring.
Embodiment 3
The high-strength polyurethane urea hydrogel that the present embodiment provides.The concrete steps of its synthetic method are as follows:
Be add the different benzene cyanate of vulcabond 1,3-bis-in the PEG acetone soln of 200g/mol at molecular weight, then add 5 μ l catalyst pyridine, at 80 DEG C, react 3h.And then diamines is added in reaction flask
, nitrogen protection stirring reaction 3h at 40 DEG C.The mol ratio of strict control reaction raw materials, i.e. PEG ︰ bis-Yi Qing Suan Zhi ︰ diamines=1 ︰ 2 ︰ 1.After reaction terminates, the solution that the viscosity obtained is very large is precipitated out in normal hexane, obtains white fluffy solid.Product is carried out moltenly after drying then pour die for molding into in methyl alcohol, after solvent evaporates is dried, be allowed to condition in distilled water swelling until reach swelling equilibrium, just obtain the hydrogel of polyurethane-urea.
The feature of the present embodiment uses aromatic vulcabond and low-molecular-weight PEG to react, and then with the diamine reactant synthesis of polyurethane urea hydrogel of aliphatics band side base.
Embodiment 4
A kind of high-strength polyurethane urea hydrogel that the present embodiment provides, synthetic route is as follows:
；
In formula, R represents alkyl in vulcabond between two isocyanos or aromatic base, and R ' represents alkyl in diamines between two amidos or aromatic base,
represent polyoxyethylene glycol (PEG), its molecular weight is 200 ~ 20000g/mol; N is the polymerization degree.
The concrete steps of synthesis are:
The first step is add N in the organic solution of the PEG of 2000g/mol, N '-dicarbapentaborane diimidazole at molecular weight; ambient temperature under nitrogen is protected, stirring reaction 30h, is precipitated by solution after reaction terminates in ether; obtain white powder precipitation, after suction filtration falls ether, product is dry.
Second step, the product chloroform the first step obtained adds H after dissolving
2n-(CH
2)
12-NH
2, make the Ju Yi bis-Chun ︰ H of initial reaction
2n-(CH
2)
12-NH
2=1 ︰ 16(mol ratio).Under nitrogen protection, room temperature reaction 72h, must arrive the macromole that two ends are amidos, centrifugal for product rear diatomite filtration is fallen upper strata solid and obtains water white transparency clear liquid, precipitated by the clear liquid obtained in ether, obtain white powdery solid diamines.
3rd step, adds OCN-(CH in the diamines of second step synthesis
2)
6-NCO, makes the Ju Yi bis-Chun ︰ vulcabond=1 ︰ 1(mol ratio of initial reaction), nitrogen protection stirring reaction 5h at 50 DEG C.After reaction terminates, the solution that the viscosity obtained is very large is precipitated out in ether, obtains white fluffy solid.Product is carried out moltenly after drying then pour die for molding into in chloroform, after solvent evaporates is dried, be allowed to condition in distilled water swelling until reach swelling equilibrium, just obtain the hydrogel of polyurethane-urea.
The feature of the present embodiment at the amine being first synthetic macromolecule, the PEG utilizing molecular weight to be 4000g/mol and the diamines H of aliphatic chain
2n-(CH
2)
12-NH
2, then with the di-isocyanate reaction of aliphatic chain, finally obtain the macromole polyurethane-urea of line style.
See the rheological diagram that accompanying drawing 8, Fig. 8 is the polyurethane-urea hydrogel that the polyoxyethylene glycol using molecular weight to be 2000g/mol in the present embodiment synthesizes.In figure, G ' Young's modulus curve is also be in G " top of loss moduli curve; and the Young's modulus of correspondence is about 50kPa; illustrate that the intensity of the hydrogel of the polyurethane-urea that this route synthesizes and the hydrogel using small molecule amine chainextender route synthesize is on an order of magnitude, proves that the method for two kinds of polyurethane-urea hydrogels synthesized provided by the invention can reach good mechanical property.
See accompanying drawing 9, it is polyurethane-urea hydrogel that the present embodiment the provides DSC graphic representation measured when different moisture content.As can be seen from Figure, along with the increase of water content, the fusing point of crystallizing field reduces gradually.Here it is, and polyurethane-urea hydrogel can have the reason of water-responsive shape memory function, namely relies on extraneous water to change the transition temperature of crystallizing field, thus can reach the function recovering initial original-shape more than certain water content.
Embodiment 5
The synthetic method of a kind of high-strength polyurethane urea hydrogel that the present embodiment provides, concrete steps are as follows:
Be add N in the DMF of the PEG of 20000g/mol, N '-dicarbapentaborane diimidazole at molecular weight, under room temperature, nitrogen protection, stirring reaction 30h, precipitates solution in normal heptane after reaction terminates, after suction filtration falls solvent, product is dry.Then after the product of the first step being dissolved with chloroform, add Isosorbide-5-Nitrae-diamino-cyclohexane, make the Ju Yi bis-Chun ︰ Isosorbide-5-Nitrae-diamino-cyclohexane=1 ︰ 16(mol ratio of initial reaction).Under nitrogen protection, room temperature reaction 72h, must arrive the macromole that two ends are amidos, centrifugal for product rear diatomite filtration is fallen upper strata solid and obtains water white transparency clear liquid, precipitated by the clear liquid obtained, obtain white powdery solid in ether.3rd step adds the different benzene cyanate of 1,3-bis-in the diamines of second step synthesis, makes the Ju Yi bis-Chun ︰ vulcabond=1 ︰ 1(mol ratio of initial reaction), nitrogen protection stirring reaction 3h at 60 DEG C.After reaction terminates, the solution that the viscosity obtained is very large is precipitated out in ether, obtains white fluffy solid.Product is carried out moltenly after drying then pour die for molding into in chloroform, after solvent evaporates is dried, be allowed to condition in distilled water swelling until reach swelling equilibrium, just obtain the hydrogel of polyurethane-urea.
The feature of the present embodiment is the macromole of two end band amidos of the diamines synthetic macromolecule first utilizing PEG and ring-type, then allow its again with aromatic di-isocyanate reaction, thus synthesize final polyurethane-urea hydrogel.
Claims (8)
1. prepare a method for polyurethane-urea hydrogel, it is characterized in that comprising the steps:
(1) be dissolved in organic solution A by polyoxyethylene glycol, described organic solvent A is the one in DMF, acetone, chloroform, methylene dichloride, ethylene dichloride; Add vulcabond and catalyzer again, described catalyzer is the one in stannous octoate, dibutyl tin laurate, N-ethylmorpholine, N-methylmorpholine, pyridine, N, N '-lutidine; Be react 1 ~ 5 hour under the condition of 20 ~ 80 DEG C in temperature, in molar ratio, Ju Yi bis-Chun ︰ vulcabond is 1 ︰ 2;
(2) adding chainextender diamine monomer, is 20 ~ 80 DEG C in temperature, stirred under nitrogen atmosphere reaction 1 ~ 5 hour, and in molar ratio, Ju Yi bis-Chun ︰ bis-Yi Qing Suan Zhi ︰ diamines is 1 ︰ 2 ︰ 1;
(3) product is placed in organic solvent B after terminating by reaction, and described organic solvent B is the one in normal hexane, normal heptane, isohexane, isoheptane, hexanaphthene, ether, obtains white fluffy solid throw out; Be dissolved in again after drying in organic solvent C, described organic solvent C is the one in methyl alcohol, ethanol, chloroform or methylene dichloride, pours die for molding into, after solvent evaporates is dried, swelling until reach swelling equilibrium in distilled water, obtain a kind of polyurethane-urea hydrogel.
2. a kind of method preparing polyurethane-urea hydrogel according to claim 1, is characterized in that: the molecular weight of described polyoxyethylene glycol is 200 ~ 20000g/mol.
3. a kind of method preparing polyurethane-urea hydrogel according to claim 1, is characterized in that: described vulcabond is the vulcabond ONC-(CH of aliphatic chain
2)
4-NCO, ONC-(CH
2)
6-NCO, ONC-(CH
2)
8-NCO, ONC-(CH
2)
12one in-NCO, 1,5-bis-isocyanic acid-2-methylpentane, or be alicyclic vulcabond
,
,
,
in one, or be aromatic vulcabond
,
,
,
,
in one.
4. a kind of method preparing polyurethane-urea hydrogel according to claim 1, is characterized in that:
Described chainextender diamine monomer is
,
,
,
, H
2n-(CH
2)
4-NH
2, H
2n-(CH
2)
6-NH
2, H
2n-(CH
2)
8-NH
2, H
2n-(CH
2)
10-NH
2in one.
5. prepare a method for polyurethane-urea hydrogel, it is characterized in that comprising the steps:
(1) be dissolved in organic solution A by polyoxyethylene glycol, described organic solvent A is the one in DMF, acetone, chloroform, methylene dichloride, ethylene dichloride; In molar ratio, add excessive N again, N '-carbonyl dimidazoles, fully react under room temperature, nitrogen protection condition, precipitated in organic solvent B by solution after end, described organic solvent B is the one in normal hexane, normal heptane, isohexane, isoheptane, hexanaphthene, ether; By obtain white powder throw out suction filtration, drying;
(2) product that step (1) obtains is dissolved in organic solution A, in molar ratio, add excessive chainextender diamine monomer, after fully reacting under room temperature, nitrogen protection condition, through centrifugal, filtration, obtain water white transparency clear liquid, be placed in organic solution C and precipitate, described organic solvent C is the one in methyl alcohol, ethanol, chloroform or methylene dichloride, obtains white powdery solid;
(3) be dissolved in organic solution A by the product that step (2) obtains, then add vulcabond, in molar ratio, Ju Yi bis-Chun ︰ vulcabond is 1 ︰ 1,25 ~ 60 DEG C, react under nitrogen protection condition;
(4) product that step (3) obtains is placed in ether to precipitate, obtains white fluffy solid, be dissolved in chloroform after drying, pour die for molding into, after solvent evaporates is dried, swelling until reach swelling equilibrium in distilled water, obtain a kind of polyurethane-urea hydrogel.
6. a kind of method preparing polyurethane-urea hydrogel according to claim 5, is characterized in that: the molecular weight of described polyoxyethylene glycol is 200 ~ 20000g/mol.
7. a kind of method preparing polyurethane-urea hydrogel according to claim 5, is characterized in that: described vulcabond is the vulcabond ONC-(CH of aliphatic chain
2)
4-NCO, ONC-(CH
2)
6-NCO, ONC-(CH
2)
8-NCO, ONC-(CH
2)
12one in-NCO, 1,5-bis-isocyanic acid-2-methylpentane, or be alicyclic vulcabond
,
,
,
in one, or be aromatic vulcabond
,
,
,
,
in one.
8. a kind of method preparing polyurethane-urea hydrogel according to claim 5, is characterized in that: described chainextender diamine monomer is
,
,
,
, H
2n-(CH
2)
4-NH
2, H
2n-(CH
2)
6-NH
2, H
2n-(CH
2)
8-NH
2, H
2n-(CH
2)
10-NH
2in one.
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