CN103524697A - Polyurethaneurea hydrogel and preparation methods therefor - Google Patents
Polyurethaneurea hydrogel and preparation methods therefor Download PDFInfo
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- C08G18/30—Low-molecular-weight compounds
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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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- C08J3/00—Processes of treating or compounding macromolecular substances
- 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
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Abstract
The invention relates to polyurethaneurea hydrogel and preparation methods therefor. The preparation methods comprise two preparation methods. The first preparation methods is as follows: diisocyanate and catalysts are added in a polyethylene glycol (PEG) organic solution for reaction, then diamine chain extender is added, and products are obtained in the organic solvent after precipitation, wherein, the molar ratio of PEG, diisocyanate and diamine is 1:2:1. The second preparation method is as follows: N,N'-dicarbonyl diimidazole is added in a PEG organic solution for reaction, then excess diamine chain extender is added, macromolecules with amidogens at two ends are obtained, finally, diisocyanate is added, and products are obtained in the organic solvent after precipitation, wherein, the molar ratio of PEG and diisocyanate is 1:2. The polyurethaneurea hydrogel has advantages of large elongation and high tensile strength, and has shape memory functions. The polyurethaneurea hydrogel has application prospects at aspects of biomedical hydrogel, tissue engineering, hydrogel support materials, biomedical devices with shape memory functions and the like.
Description
Technical field
The present invention relates to biological medical polymer material and supramolecular chemistry field, relate in particular to and a kind ofly there is good mechanical property and can realize water or the polyurethane-urea hydrogel of thermo-responsive shape memory function and preparation method thereof.
Background technology
Hydrogel be a kind of in water swelling, 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, the replacement of pharmaceutical carrier, wound dressing, cartilage, artificial kidney film and other medical devices.But because hydrogel is when the swollen state, be usually expressed as weak mechanical property, so its application is limited by very large.Because as bio-medical material, except need have certain biological similarity and consistency, also need to have the deformation restorability under good physical strength, stability and External Force Acting.The method of traditional raising hydrogel mechanical property is mainly to depend on the density that improves chemically crosslinked point, and still improving cross-linking set can cause the reduction of water-intake rate conventionally, and it is very loaded down with trivial details to remove the process of unreacted linking agent.Due to above these restrictions, the hydrogel of physical crosslinking starts to be paid close attention to widely.Document (Macromolecules, 2010,43,7637 – 7649) reported a kind of hydrogel, soft section of hydrophilic polyoxyethylene glycol (PEG) has been 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, thereby forms organic-inorganic compounding network, and its shearing modulus reaches as high as 4.0 MPa, but because it is composite organic-inorganic material, therefore Shortcomings aspect the consistency of material.
In polyurethane-urea hydrogel, contain carbamate groups and urea groups, 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, thereby are conducive to the enhancing of the intensity of synthetic hydrogel.But owing to containing a large amount of water moleculess in hydrogel, in forming the process of hydrogen bond, water can be competed with the hydrogen bond of polyurethane-urea self, to such an extent as to hydrogen bond reduced number in hydrogel self structure, so most of synthetic polyurethane-urea hydrogel intensity is very low.Document (Biomacromolecules, 2012,13,3966 3976) reported a kind of very stable injectable PEG-urea block copolymer hydrogel in water that relies on that synergy between multiple hydrogen bonding and hydrophobic interaction power forms, by regulating the density of physics cross-linking set and the length of hydrophobic segment, its modulus can regulate between 0.4～20 kPa.But because the hydrophobic aggregation effect forming in molecule is not very strong, from form, this hydrogel is still rarer glutinous, is difficult to sizing, much need high mechanical strength application aspect thereby be restricted.
In addition, need the bio-medical material of implant into body in use, how to make the wound that in implantation process, patient caused minimum, after implanting, how to take out, also receive increasing concern.The artificial device of shape-memory polymer (SMPs) type has met the demand of this respect just.This be because, the SMPs goods with certain original shape, can under specific work program, produce required deformation, be prepared into the interim shape that is applicable to Minimally Invasive Surgery, after this interim shape implants, can under external stimulus (as hot, optical, electrical, magnetic and solvent etc.), return to its original shape.But the deformation of current all SMPs (comprising currently reported water-responsive SMPs) produce all need be at higher temperature the (T of polymkeric substance
gor T
mcarry out above), easily cause the activity of the bioactive ingredients (as albumen and medicine etc.) of material surface or inside greatly to reduce, even lost efficacy.Meanwhile, the SMPs of the overwhelming majority is thermosensitive type at present, and its deformation recovers also need at higher temperature, carry out, and easily implant site tissue is around caused to damage.Publication number be WO 2012/168392 A1 PCT patent report the hydrogel of shape memory of a kind of water and hot double-response function, be characterized in the hydrogel of dry state to be heated to 70 ℃, make it change elastomeric state into, and then under elastomeric state, design a transient state shape, after temperature drops to below transition temperature, this interim shape is fixed, and then returns to original shape under the stimulation of water or heat.
Summary of the invention
Problem to be solved by this invention is to overcome the weak deficiency of physical strength that in prior art, synthesis of polyurethane urea hydrogel exists, provide a kind of synthetic method simple, physical strength is high, applied widely, and the shape memory function simultaneously with temperature and water-responsive, 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 or the aromatic base between two isocyanos in vulcabond, R ' is alkyl or the aromatic base between two amidos in diamines,
for polyoxyethylene glycol, n is the polymerization degree.
Above-described polyurethane-urea hydrogel, the elongation at break of its stretching is 200～2000 %; Tensile strength is 10～2000 kPa.
The intensity that the hydrogel based multiple hydrogen bonding in urea groups of polyurethane-urea provided by the invention and the synergistic method of hydrophobic aggregation strengthen polyurethane-urea hydrogel.
The preparation of the polyurethane-urea hydrogel the present invention relates to, can realize by following two routes:
Or
In formula, R represents alkyl or the aromatic base between two isocyanos in vulcabond, and R ' represents alkyl or the aromatic base between two amidos in diamines,
represent polyoxyethylene glycol (PEG), n is the polymerization degree.
The first preparation method's concrete steps are as follows:
(1) polyoxyethylene glycol is dissolved in organic solution A, described organic solvent A is a kind of in DMF, acetone, chloroform, methylene dichloride, ethylene dichloride; Add vulcabond and catalyzer, described catalyzer is stannous octoate, dibutyl tin laurate, N-ethylmorpholine, N-methylmorpholine, pyridine, N again, a kind of in N '-lutidine; In temperature, be to react 1 ~ 5 hour under the condition of 20 ~ 80 ℃, in molar ratio, Ju Yi bis-Chun ︰ vulcabond is 1 ︰ 2;
(2) adding chainextender diamine monomer, is 20 ~ 80 ℃ in temperature, and under nitrogen protection, stirring reaction is 1 ~ 5 hour, and in molar ratio, Ju Yi bis-Chun ︰ bis-Yi Qing Suan Zhi ︰ diamines is 1 ︰ 2 ︰ 1;
(3) reaction is placed in organic solvent B by product after finishing, and described organic solvent B is a kind of in normal hexane, normal heptane, isohexane, isoheptane, hexanaphthene, ether, obtains white cotton-shaped solid sediment; After dry, be dissolved in again in organic solvent C, described organic solvent C is a kind of in methyl alcohol, ethanol, chloroform or methylene dichloride, pours die for molding into, after solvent evaporates is dried, swelling in distilled water until reach swelling equilibrium, obtains a kind of polyurethane-urea hydrogel.
The concrete steps of method that another kind is prepared polyurethane-urea hydrogel are as follows:
(1) polyoxyethylene glycol is dissolved in organic solution A, described organic solvent A is a kind of in DMF, acetone, chloroform, methylene dichloride, ethylene dichloride; In molar ratio, add again excessive N, N '-dicarbapentaborane diimidazole, fully reaction under room temperature, nitrogen protection condition, after end, solution is precipitated in organic solvent B, described organic solvent B is a kind of in normal hexane, normal heptane, isohexane, isoheptane, hexanaphthene, ether; By the white powdery throw out suction filtration obtaining, dry;
(2) product step (1) being obtained 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 a kind of in methyl alcohol, ethanol, chloroform or methylene dichloride, obtains white powdery solid;
(3) product step (2) being obtained is dissolved in organic solution A, then adds vulcabond, and in molar ratio, Ju Yi bis-Chun ︰ vulcabond is 1 ︰ 1, under 25 ~ 60 ℃, nitrogen protection condition, reacts;
(4) product step (3) being obtained is placed in ether and precipitates, and obtains white cotton-shaped solid, after being dried, is dissolved in chloroform, pour die for molding into, after solvent evaporates is dried, swelling in distilled water until reach swelling equilibrium, obtains a kind of polyurethane-urea hydrogel.
The molecular weight of polyoxyethylene glycol described in technical solution of the present invention is 200～20000 g/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)
12-NCO, 1, a kind of in 5-bis-isocyanic acids-2-methylpentane, or be alicyclic vulcabond
,
,
,
in a kind of, or be aromatic vulcabond
,
,
,
,
in a kind of.
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 a kind of.
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 a kind of.
Owing to having implemented technique scheme, compared with prior art, the invention has the advantages that:
1, because synthetic product is linear molecule, dissolve in many organic solvents or carry out melt-processed, greatly facilitate its processed and applied.And introduced a large amount of carbamate groups and urea groups, between them, can form multiple hydrogen bonding, this intermolecular reactive force can effectively provide the mechanical property of hydrogel.
2, when gel state, the hydrophobic microcell that the hydrophobic chain self-assembly on urea groups both sides forms wraps up hydrogen bond group, water in itself and hydrophilic polymer chains and gel network is kept apart, reach the effect that strengthens hydrogen bond, these interaction of hydrogen bond power that strengthened can make again the hydrophobic shell of its periphery more closely assemble, and realize the synergistic enhancing effect between hydrogen bond and hydrophobic aggregation reactive force.
When 3, the synthetic polyurethane-urea hydrogel of the present invention has temperature response shape memory function, there is again water-responsive shape memory function under room temperature.The crystallization phases that meanwhile, also can rely on the good tensile property of made hydrogel and PEG to follow in process is decrystallized in dehydration crystallization-water suction changes to realize that 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 provides of the embodiment of the present invention 1;
Fig. 2 is the nuclear magnetic spectrogram of the polyurethane-urea hydrogel that provides of the embodiment of the present invention 1;
Fig. 3 is the stress strain diagrm of the tension test of the polyurethane-urea hydrogel that provides of the embodiment of the present invention 1;
Fig. 4 be the polyurethane-urea hydrogel that provides of the embodiment of the present invention 1 300% under the stress strain diagrm of five cyclic tensions tests;
Fig. 5 be the polyurethane-urea hydrogel that provides of the embodiment of the present invention 1 200% under the stress strain diagrm of five cyclic tensions tests;
Fig. 6 be the polyurethane-urea hydrogel that provides of the embodiment of the present invention 1 100% under the stress strain diagrm of five cyclic tensions tests;
Fig. 7 is that use molecular weight that the embodiment of the present invention 1 provides is the rheometer test figure of the synthetic polyurethane-urea hydrogel of the polyoxyethylene glycol of 4000 g/mol;
Fig. 8 is that use molecular weight that the embodiment of the present invention 4 provides is the rheometer test figure of the synthetic polyurethane-urea hydrogel of the polyoxyethylene glycol of 2000 g/mol;
Fig. 9 is the DSC test curve figure of the polyurethane-urea hydrogel that provides of the embodiment of the present invention 4 when different moisture content.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further elaborated.
A kind of high-strength polyurethane urea hydrogel that the present embodiment provides, its synthetic route is:
In formula, R represents alkyl or the aromatic base between two isocyanos in vulcabond, and R ' represents alkyl or the aromatic base between two amidos in diamines,
represent polyoxyethylene glycol (PEG), its molecular weight is 200 ~ 20000 g/mol; N is the polymerization degree.
Synthetic concrete steps are: in molecular weight is the DMF solution of PEG of 4000 g/mol, add vulcabond OCN-(CH
2)
12-NCO, then add 5 μ l catalyzer dibutyl tin laurates, reacts 2 h at 80 ℃.And then add diamines H in reaction flask
2n-(CH
2)
6-NH
2, stirring reaction 3 h under 20 ℃, nitrogen protection.The strict mol ratio of controlling reaction raw materials, i.e. PEG ︰ bis-Yi Qing Suan Zhi ︰ diamines=1 ︰ 2 ︰ 1.After reaction finishes, the very large solution of the viscosity obtaining is precipitated out in normal hexane, obtains white cotton-shaped solid.Molten in ethanol after product is dried, then pour die for molding into, after solvent evaporates is dried, be allowed to condition at swelling in distilled water until reach swelling equilibrium, just obtained the hydrogel of polyurethane-urea.
Referring to accompanying drawing 1, it is the infrared spectrum of the polyurethane-urea hydrogel that provides of the present embodiment; Visible in figure, 2850 cm
-1: methylene peak; 1670-1690 cm
-1: allophanyl; 1530 cm
-1: carbamate eigen vibration peak.
Referring to accompanying drawing 2, it is the nuclear magnetic spectrogram of the polyurethane-urea hydrogel that provides of the present embodiment; Test condition is CDCl3, h400,
1h-NMR (400 MHz, CDCl
3); δ=7.26 (solvent peak, CDCl wherein
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 aliphatic chain and the macromole polyurethane-urea hydrogel of the synthetic line style of diamines for the present embodiment, have following structure:
In formula, R represents alkyl or the aromatic base between two isocyanos in vulcabond, and R ' represents alkyl or the aromatic base between two amidos in diamines,
represent polyoxyethylene glycol (PEG), its molecular weight is 200 ~ 20000 g/mol; N is the polymerization degree.In the long chain molecule of this linearity, contain a large amount of urea groups, between urea groups, can form a large amount of hydrogen bonds, the hydrophobic microcell that hydrophobic chain self-assembly in molecule forms simultaneously wraps up hydrogen bond group, water in itself and hydrophilic polymer chains and gel network is kept apart, reach the effect that strengthens hydrogen bond, these interaction of hydrogen bond power that strengthened can make again the hydrophobic shell of its periphery more closely assemble, realize the synergistic enhancing effect between hydrogen bond and hydrophobic aggregation reactive force, therefore, mechanicalness is effectively improved.
Referring to accompanying drawing 3, it is the Elongation test graphic representation of the polyurethane-urea hydrogel that provides of the present embodiment, and as can be seen from Figure, its elongation at break is 1320 %, and corresponding stress is 2000 kPa.Namely, just can rupture in 13 times of left and right that this hydrogel can be moved former length to, and the highest drawing force bearing is 2000 kPa.The scope of its elongation at break of product that the present invention is synthetic can regulate in 200 % ~ 2000 %, and this high-intensity character is likely applied to the biomaterials such as replacement of tissue engineering bracket and cartilage.
Referring to accompanying drawing 4, it is the cyclic tension test curve figure of the polyurethane-urea hydrogel that provides of the present embodiment, and Fig. 4, Fig. 5, Fig. 6 are respectively five cyclic tensions tests under 300 %, 200 %, 100 %.As seen from the figure, 300 %, 200 % cyclic tension tests are in the process of first circulation, all there is energy waste to a certain degree in sample, 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 respectively 80 % and 88 % of former length.Circulate in the position that all can not be returned to original stress under same strain 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, makes 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 while being very large, sample can be returned to former length substantially.
Referring to accompanying drawing 7, it is the rheometer test figure of the polyurethane-urea hydrogel that provides of the present embodiment; X-coordinate is circular frequency, and ordinate zou is stress, and two lines are respectively Young's modulus and stickiness modulus with the curve of angular velocity varies.Fig. 7 is that to use molecular weight be the rheological diagram of the synthetic polyurethane-urea hydrogel of the polyoxyethylene glycol of 4000 g/mol.As can be seen from the figure, G ' Young's modulus curve is all the time in G " top of stickiness modulus curve, illustrate that this hydrogel has shown the character of solid, and its Young's modulus is about 45 kPa, also reflected that the strength ratio of 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: will after polyurethane-urea swelling behavior, be designed to original shape, utilize the stretching-dehydration at room temperature of its snappiness after its swelling after, obtain interim shape, the dry state gel of the interim shape after fixing is put into after 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: will after polyurethane-urea swelling behavior, be designed to original shape, after polyurethane-urea hydrogel is heated to 50 ℃, it is stretched and obtains interim shape, the dry state gel of the interim shape after fixing is put into 50 ℃ of silicone oil, its shape returns to original shape, realizes the memory function of shape.
The present embodiment provides a kind of synthetic method of high-strength polyurethane urea hydrogel, and concrete steps are as follows:
In molecular weight is the PEG acetone soln of 10000 g/mol, add vulcabond IPDI, then add the sub-tin of 5 μ l octoate catalysts, react 3 h at 50 ℃.And then in reaction flask, add diamines 3,3 '-methylene pentanoic, nitrogen protection stirring reaction 3 h at 40 ℃.The strict mol ratio of controlling reaction raw materials, i.e. PEG ︰ bis-Yi Qing Suan Zhi ︰ diamines=1 ︰ 2 ︰ 1.After reaction finishes, the very large solution of the viscosity obtaining is precipitated out in ether, obtains white cotton-shaped solid.Molten in chloroform after product is dried, then pour die for molding into, after solvent evaporates is dried, be allowed to condition at swelling in distilled water until reach swelling equilibrium, just obtained the hydrogel of polyurethane-urea.
The feature of the present embodiment is to use the PEG that alicyclic vulcabond IPDI is 6000 g/mol with molecular weight to react, and then with aromatic diamine synthesis of polyurethane urea hydrogel with phenyl ring.
The high-strength polyurethane urea hydrogel that the present embodiment provides.The concrete steps of its synthetic method are as follows:
In molecular weight is the PEG acetone soln of 200 g/mol, add vulcabond 1, the different benzene cyanate of 3-bis-, then add 5 μ l catalyzer pyridines, reacts 3 h at 80 ℃.And then add diamines in reaction flask
, nitrogen protection stirring reaction 3 h at 40 ℃.The strict mol ratio of controlling reaction raw materials, i.e. PEG ︰ bis-Yi Qing Suan Zhi ︰ diamines=1 ︰ 2 ︰ 1.After reaction finishes, the very large solution of the viscosity obtaining is precipitated out in normal hexane, obtains white cotton-shaped solid.Molten in methyl alcohol after product is dried, then pour die for molding into, after solvent evaporates is dried, be allowed to condition at swelling in distilled water until reach swelling equilibrium, just obtained the hydrogel of polyurethane-urea.
The feature of the present embodiment is to use aromatic vulcabond to react with low-molecular-weight PEG, and then with the diamine reactant synthesis of polyurethane urea hydrogel of aliphatics band side group.
A kind of high-strength polyurethane urea hydrogel that the present embodiment provides, synthetic route is as follows:
In formula, R represents alkyl or the aromatic base between two isocyanos in vulcabond, and R ' represents alkyl or the aromatic base between two amidos in diamines,
represent polyoxyethylene glycol (PEG), its molecular weight is 200 ~ 20000 g/mol; N is the polymerization degree.
Synthetic concrete steps are:
The first step adds N, N '-dicarbapentaborane diimidazole in molecular weight is the organic solution of PEG of 2000 g/mol; nitrogen protection under room temperature, stirring reaction 30 h precipitate solution after reaction finishes in ether; obtain white powdery precipitation, suction filtration falls after ether, and product is dry.
Second step, the product that the first step is obtained adds H after dissolving with chloroform
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 72 h, must arrive two ends is macromole of amido, with diatomite filtration, falls upper strata solid and obtains water white transparency clear liquid afterwards product is centrifugal, and the clear liquid obtaining is precipitated in ether, obtains white powdery solid diamines.
The 3rd step adds OCN-(CH in the synthetic diamines of second step
2)
6-NCO, makes the Ju Yi bis-Chun ︰ vulcabond=1 ︰ 1(mol ratio of initial reaction), nitrogen protection stirring reaction 5 h at 50 ℃.After reaction finishes, the very large solution of the viscosity obtaining is precipitated out in ether, obtains white cotton-shaped solid.Molten in chloroform after product is dried, then pour die for molding into, after solvent evaporates is dried, be allowed to condition at swelling in distilled water until reach swelling equilibrium, just obtained the hydrogel of polyurethane-urea.
The feature of the present embodiment is at the amine that is first synthetic macromolecule, and utilizing molecular weight is the PEG of 4000 g/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.
Referring to accompanying drawing 8, Fig. 8 is that in the present embodiment, to use molecular weight be the rheological diagram of the synthetic polyurethane-urea hydrogel of the polyoxyethylene glycol of 2000 g/mol.In figure, G ' Young's modulus curve is also in G " top of stickiness modulus curve; and corresponding Young's modulus is about 50 kPa; illustrate that the intensity of the hydrogel that the hydrogel of the polyurethane-urea that this route is synthetic is synthetic with using small molecule amine chainextender route, on an order of magnitude, proves that the method for two kinds of synthetic polyurethane-urea hydrogels provided by the invention can reach good mechanical property.
Referring to accompanying drawing 9, it is the polyurethane-urea hydrogel that provides of the present embodiment measured DSC graphic representation 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, relies on extraneous water to change the transition temperature of crystallizing field, thereby can more than certain water content, reach the function of recovering initial original-shape.
The synthetic method of a kind of high-strength polyurethane urea hydrogel that the present embodiment provides, concrete steps are as follows:
In being the DMF of PEG of 20000 g/mol, molecular weight adds N, N '-dicarbapentaborane diimidazole, and under room temperature, nitrogen protection, stirring reaction 30 h precipitate solution after reaction finishes in normal heptane, and suction filtration falls after solvent, and 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 72 h, must arrive two ends is macromole of amido, with diatomite filtration, falls upper strata solid and obtains water white transparency clear liquid afterwards product is centrifugal, and the clear liquid obtaining is precipitated in ether, obtains white powdery solid.The 3rd step is in the synthetic diamines of second step, to add the different benzene cyanate of 1,3-bis-, makes the Ju Yi bis-Chun ︰ vulcabond=1 ︰ 1(mol ratio of initial reaction), nitrogen protection stirring reaction 3 h at 60 ℃.After reaction finishes, the very large solution of the viscosity obtaining is precipitated out in ether, obtains white cotton-shaped solid.Molten in chloroform after product is dried, then pour die for molding into, after solvent evaporates is dried, be allowed to condition at swelling in distilled water until reach swelling equilibrium, just obtained the hydrogel of polyurethane-urea.
The feature of the present embodiment is first to utilize the macromole of two ends band amido of the diamines synthetic macromolecule of PEG and ring-type, then allow its again with aromatic di-isocyanate reaction, thereby synthetic final polyurethane-urea hydrogel.
Claims (10)
1. a polyurethane-urea hydrogel, is characterized in that: described hydrogel is the multipolymer of polyoxyethylene glycol, vulcabond and diamines, and its structural formula is:
2. a kind of polyurethane-urea hydrogel according to claim 1, is characterized in that: the elongation at break of its stretching is 200～2000%; Tensile strength is 10～2000kPa.
3. a method of preparing polyurethane-urea hydrogel as claimed in claim 1 or 2, is characterized in that comprising the steps:
(1) polyoxyethylene glycol is dissolved in organic solution A, described organic solvent A is a kind of in DMF, acetone, chloroform, methylene dichloride, ethylene dichloride; Add vulcabond and catalyzer, described catalyzer is stannous octoate, dibutyl tin laurate, N-ethylmorpholine, N-methylmorpholine, pyridine, N again, a kind of in N '-lutidine; In temperature, be to react 1～5 hour under the condition of 20～80 ℃, in molar ratio, Ju Yi bis-Chun ︰ vulcabond is 1 ︰ 2;
(2) adding chainextender diamine monomer, is 20～80 ℃ in temperature, and under nitrogen protection, stirring reaction is 1～5 hour, and in molar ratio, Ju Yi bis-Chun ︰ bis-Yi Qing Suan Zhi ︰ diamines is 1 ︰ 2 ︰ 1;
(3) reaction is placed in organic solvent B by product after finishing, and described organic solvent B is a kind of in normal hexane, normal heptane, isohexane, isoheptane, hexanaphthene, ether, obtains white cotton-shaped solid sediment; After dry, be dissolved in again in organic solvent C, described organic solvent C is a kind of in methyl alcohol, ethanol, chloroform or methylene dichloride, pours die for molding into, after solvent evaporates is dried, swelling in distilled water until reach swelling equilibrium, obtains a kind of polyurethane-urea hydrogel.
4. a kind of method of preparing polyurethane-urea hydrogel according to claim 3, is characterized in that: the molecular weight of described polyoxyethylene glycol is 200～20000g/mol.
5. a kind of method of preparing polyurethane-urea hydrogel according to claim 3, is characterized in that: the vulcabond ONC-(CH that described vulcabond is aliphatic chain
2)
4-NCO, ONC-(CH
2)
6-NCO, ONC-(CH
2)
8-NCO, ONC-(CH
2)
12-NCO, 1, a kind of in 5-bis-isocyanic acids-2-methylpentane, or be alicyclic vulcabond
in a kind of, or be aromatic vulcabond
in a kind of.
6. a kind of method of preparing polyurethane-urea hydrogel according to claim 3, 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 a kind of.
7. a method of preparing polyurethane-urea hydrogel as claimed in claim 1 or 2, is characterized in that comprising the steps:
(1) polyoxyethylene glycol is dissolved in organic solution A, described organic solvent A is a kind of in DMF, acetone, chloroform, methylene dichloride, ethylene dichloride; In molar ratio, add again excessive N, N '-dicarbapentaborane diimidazole, fully reaction under room temperature, nitrogen protection condition, after end, solution is precipitated in organic solvent B, described organic solvent B is a kind of in normal hexane, normal heptane, isohexane, isoheptane, hexanaphthene, ether; By the white powdery throw out suction filtration obtaining, dry;
(2) product step (1) being obtained 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 a kind of in methyl alcohol, ethanol, chloroform or methylene dichloride, obtains white powdery solid;
(3) product step (2) being obtained is dissolved in organic solution A, then adds vulcabond, and in molar ratio, Ju Yi bis-Chun ︰ vulcabond is 1 ︰ 1, under 25～60 ℃, nitrogen protection condition, reacts;
(4) product step (3) being obtained is placed in ether and precipitates, and obtains white cotton-shaped solid, after being dried, is dissolved in chloroform, pour die for molding into, after solvent evaporates is dried, swelling in distilled water until reach swelling equilibrium, obtains a kind of polyurethane-urea hydrogel.
8. a kind of method of preparing polyurethane-urea hydrogel according to claim 7, is characterized in that: the molecular weight of described polyoxyethylene glycol is 200～20000g/mol.
9. a kind of method of preparing polyurethane-urea hydrogel according to claim 7, is characterized in that: the vulcabond ONC-(CH that described vulcabond is aliphatic chain
2)
4-NCO, ONC-(CH
2)
6-NCO, ONC-(CH
2)
8-NCO, ONC-(CH
2)
12-NCO, 1, a kind of in 5-bis-isocyanic acids-2-methylpentane, or be alicyclic vulcabond
in a kind of, or be aromatic vulcabond
in a kind of.
10. a kind of method of preparing polyurethane-urea hydrogel according to claim 7, 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 a kind of.
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