WO2012168392A1 - Hydrogélifiant ayant des propriétés de mémoire de forme - Google Patents

Hydrogélifiant ayant des propriétés de mémoire de forme Download PDF

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Publication number
WO2012168392A1
WO2012168392A1 PCT/EP2012/060841 EP2012060841W WO2012168392A1 WO 2012168392 A1 WO2012168392 A1 WO 2012168392A1 EP 2012060841 W EP2012060841 W EP 2012060841W WO 2012168392 A1 WO2012168392 A1 WO 2012168392A1
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hydrogelator
hydrogel
ureido
poly
upy
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PCT/EP2012/060841
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Mingyu GUO
Hans Markus WYSS
Patricia Yvonne Wilhelmina Dankers
Egbert Willem Meijer
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Technische Universiteit Eindhoven
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • 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
    • C08G18/5045—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing urethane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2210/00—Compositions for preparing hydrogels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2280/00—Compositions for creating shape memory

Definitions

  • the invention pertains to hydrogelators and to elastic hydrogels with thermo- and water-responsive shape-memory properties in its dehydration state.
  • a supramolecular hydrogel is a colloidal material composed of gelator molecules (low molecular weight organic compound) and water molecules.
  • the gelator molecules are arranged in such a way that they form a mesh that traps the water molecules in the interstitial spaces.
  • Such small organic molecules (low molecular weight) capable of gelling aqueous solvents are called hydrogelators.
  • Gels can be classified as either chemical or physical. Chemical gels form a molecular mesh by covalent bonds, whereas physical gels form as a result of non-covalent interactions. The majority of physical gels are made from polymeric molecules, but
  • non-polymeric molecules can also self-assemble to form aggregates that gelate solvent.
  • Many non-polymeric physical gels have been reported that are capable of forming gels in various organic solvents. Polymeric gels are common but
  • nonpolymeric physical hydrogels are rare.
  • Studies on supramolecular gels have been of considerable interest in recent years because of the many potential applications like tissue engineering, nanotechnology, used as biomaterials, vehicles for controlled drug release, pollution control etc.
  • a priori design of a gelator for the gelation of water molecules has remained a challenging task.
  • Supramolecular hydrogels are formed by the self-assembly of a small amount of hydrogelators in water through non-covalent interactions such as hydrogen bonding, ⁇ - ⁇ stacking, van der Waals interaction, coordination and so on. These non-covalent interactions endue supramolecular hydrogels with beautiful physical properties. However, these reversible non-covalent interactions often make the formed hydrogels brittle, and not suitable for the tissue engineering applications. Others are more elastic, but are then not stable in time. They show self-healing, creep etc. due to the dynamic nature of the physical bonds.
  • the materials is a nanoscopic phase-separated material .
  • shape-memory polymers are an emerging class of active polymers. They have the capability of changing their shapes from temporary shape to permanent shape upon exposed to an appropriate external stimulus.
  • Biocompatible synthetic polymers with shape memory (SM) behavior hold tremendous promise for critically important applications in the biomedical industry, including sutures and implantable stents.
  • SMPs Shape memory polymers
  • the temporary shape After macroscopic deformation from an equilibrium (i.e., permanent) shape, the temporary shape should be ideally retained until a controlled stimulus (e.g., heat, light, solvent exposure) induces recovery to the original geometry.
  • a controlled stimulus e.g., heat, light, solvent exposure
  • the permanent molecular structure typically consists of a deformable soft matrix with either physical or chemical crosslinks defining an equilibrium conformation. Shape recovery is driven by the entropic gain from chain relaxation, which is accelerated appreciably above T g or T m .
  • Thermally induced shape recovery is often achieved with a semicrystaNine polymer matrix comprising the switching domain, where the recovery transition temperature (T tr ) corresponds to crystallite melting.
  • the crystalline regions provide a
  • PEO poly(ethylene oxide)
  • PCL poly(E-caprolactone)
  • T m melting temperatures
  • T m melting temperatures
  • great effort has been exerted to modify and enhance the mechanical performance of these characteristically brittle materials, ultimately targeting products that require flexibility and ductility in addition to the implicit biocompatibility and cargo delivery capacity in certain instances.
  • the properties have been modified with chemical crosslinks, copolymerizations, etc., and pendent hydrogen bonding sites, for example.
  • Some designs contain specific, stimuli responsive degradable segments that encapsulate and subsequently release cargo, aimed at controlled drug delivery capabilities.
  • the crosslink density can be systematically varied in an effort to tune the ultimate modulus and failure elongations, which cumulatively reflect the toughness of the material. Combining toughness with high recovery has been a daunting challenge, with some recent success accomplished through complex molecular makeup.
  • the present invention discloses a newly designed hydrogelator obtained by adding a nitrogen containing heterocyclic organic compound that is substituted with at least one ureido-group, preferably only one ureido-group, to a poly(alkylene glycol) and wherein the ureido-group and the poly(alkylene glycol) are spaced by a hydrophobic linker or spacer, preferably an alkyl spacer.
  • the nitrogen containing heterocyclic organic compound can be selected at will as long as at least one H-atom on one of the carbon atoms in the ring can be substituted by the ureido group, i.e. -NH-CO-NH-group.
  • a substituted pyridine also referred to as azine or azabenzene
  • substituted derivatives of pyridine such as 2,2'-bipyridine and 1 ,10-phenanthroline can be used.
  • nitrogen containing heterocyclic organic compounds are those with two or more nitrogen atoms in the ring, such as diazines, triazines, tetraazines, pentaazines or even hexaazines.
  • diazines or triazines are selected.
  • the 1 ,3,5-triazine (with alternating carbon and nitrogen atoms in the ring) or its derivatives are preferred.
  • diazines are preferred.
  • a suitable diazine can also be selected at will as long as at least one H-atom on one of the carbon atoms in the ring can be substituted by the ureido group, i.e. -NH-CO-NH-group.
  • derivatives of diazines can be used, such as condensed diazines, e.g. purines (purine or adenine).
  • diazine derivatives cytosine (C), thymine (T), and uracil (U).
  • pyrimidine (1 ,3-diazine or m-diazine)
  • pyradizine (1 ,2-diazine or ortho-diazine
  • pyrazine (1 ,4-diazine or o-diazine)
  • pyrimidine-structure is preferred, even more preferred is pyrimidinone, sometimes also referred to as "pyrimidine” in the literature), such as 4-pyrimidinone.
  • the hydrogelator contains as the substituted diazine a 2-ureido-4[1 H]-pyrimidinone or its respective tautomer 2-ureido-4[3H]-pyrimidinone (both referred to as UPy).
  • UPy 2-ureido-4[1 H]-pyrimidinone
  • the structures can schematically be shown as follows:
  • the hydrogelator of the present invention contains an ureido-group that is chain extended.
  • the hydrogelator according to the invention contains poly(ethylene glycol) as the poly(alkylene glycol) moiety.
  • poly(alkylene glycol) also encompasses copolymers (random or block) of two or more different alkylene glycols, such as a block-copolymer of poly(ethylene glycol) and poly(propylene glycol). Multiple block-copolymers, such as
  • tribock-copolymers can also be used successfully.
  • An example is poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol).
  • Such a triblock-copolymer is commercially available, e.g. under the trademark Pluronic® from BASF AG.
  • the ureido-group and the poly(alkylene glycol) are spaced by a hydrophobic linker, such as an alkyl spacer spacer, preferably an oligomethylene, even more preferred an alkyl spacer that is (-CH 2 -)i 2 -
  • the poly(alkylene glycol) moiety is diamine terminated.
  • the hydrogelator can be obtained by adding a chain-extended
  • the hydrogelator is obtained by adding a diisocyanate of formula (I)
  • OCN-C6Hi2-UPy-C6Hi2-NCO (I) to an amino-telechelic polyethylene oxide flanked with oligomethylene spacers of formula (II): H 2 N-Ci2H2 4 (OC2H ) x Ci2H2 4 NH2 (II), wherein x is the polymerization degree of the polyethylene oxide.
  • X can be varied from 10 to 300, preferably from 50 to 250 and more preferably form 200 to 250, such as 227.
  • the obtained present hydrogelator forms a strong and elastic supramolecular hydrogel in its hydration or swelling state, and shows both reversible thermo and water responsive shape-memory properties in its dehydration state.
  • the preferred features include a strong, non-covalent interaction within domains comprising nanoscopic confluences of long PEO segments.
  • the dynamic bonding among the aggregates promotes processability, in contrast to chemical crosslinks in conventional thermoset materials. Additionally the strength could foreseeably be adjusted by implementing different lengths/composition of PEO. This could be achieved in a straightforward manner owing to the modular synthetic protocol employed.
  • the H-bonding motif allows strong, phase segregated segments to act as physical crosslinks at relatively low composition. This feature translates to low crosslink density, ultimately displaying impressively large elongation-recovery profiles with minimal diminishment of modulus compared with pristine PEO.
  • Most instances of thermoplastic SMPs rely on high T m or high T g physical crosslinking components, which require relatively high composition to maximize the strength.
  • Fig. 1 a/b shows diagrams of rheology (a) and tensile tests (b) of the hydrogel film at an elongation rate of 60 mm/min at room temperature.
  • Fig. 2 a/b shows a scheme of the thermo and water responsive shape recovery (a) and a diagram from a tensile test at 60 °C and 60 mm/min elongation rate (b) of the dehydrated CEUPy polymer film.
  • Fig. 3 shows DSC curves of the original and stretched dehydrated
  • Fig. 4 a/b shows diagrams of the temperature dependence of the G' and G" of the dehydrated (a) and hydrogel (b) films.
  • Fig. 5 shows DSC curves of the dehydrated and hydrogel films with different water ratios.
  • Fig. 6 shows a schematic representation to make a shape-memory tube and photos of the prepared tubes in all its forms.
  • Fig. 7 shows PEO-UPy (co)polymers with telechelelic (1 ) and segmented multiblock (2) architectures and (3) complementary quadruple hydrogen bonding interaction between two UPy segments.
  • Fig. 8 shows (a) DSC thermograms for the dry polymer 2 and hydrogels at various concentrations (2nd heating; 10 °C min "1 ) and photographs of (b) melt pressed film of dry polymer 2 and (c) hydrogel with 85 wt % water.
  • Fig. 10 shows cyclic stress-strain results with (a) maximum strain (£ ma x) of 100% and (b) £ ma x of 300% having 5 cycles each and (c) recovery ratio (R r ) for each cycle (N).
  • HDI-UPy-HDI diisocyanate UPy
  • DAPEG diamine-terminated poly(ethylene glycol)
  • the storage moduli, G', and loss moduli, G" of the fully swelled hydrogel, which contains 90 % water, as function of angle frequency at a fixed strain (1 .0 %) are shown in Figure 1 a.
  • the sample has a single plateau region in its dynamic moduli.
  • the G' value has a substantial elastic response and is always higher than the G" over the entire range of frequency.
  • the typical G' value is about 20 kPa, which is close to the desired modulus for soft tissue engineering and living soft tissues (on the order of 1000 Pa).
  • the present hydrogel also shows excellent elastic properties and is able to withstand strains of up 550 % before breaking.
  • the invention is also directed to a hydrogel comprising the addition reaction product of a diisocyanate of formula (I) OCN-C6Hi2-UPy-C6Hi2-NCO (I) and an amino-telechelic polyethylene oxide flanked with oligomethylene spacers of formula (II): H 2 N-Ci2H2 4 (OC2H4)xCi2H 24 NH2 (II), wherein x is the polymerization degree of the polyethylenoxide.
  • X can be varied from 10 to 300, preferably from 50 to 250 and more preferably form 200 to 250, such as 227.
  • the dehydrated hydrogel film has both thermo and water responsive shape memory properties.
  • the permanent shape was stretched at 60 °C and fixed at room temperature to yield temporary shape 1 , which could be further twisted at room temperature to yield temporary shape 2.
  • temporary shape 2 (or temporary shape 1 ) could recover to its permanent shape.
  • the dehydrated hydrogel film is able to withstand strains of up 1000 % before breaking at 60 °C and 60 mm/min elongation rate ( Figure 2b).
  • SMPs often consist of two segments/phases; one of them is a fixed phase and the other is a reversible or switching one. Thus their shape recovery effect is always accompanied with the phase transition of these domains.
  • DSC differential scanning calorimetry
  • thermo-responsive shape-memory phenomena should be contributed to the crystallization transitions of the PEG chains.
  • the crystallization domains of the PEG part functioned as the temporary physical cross-linkers and fixed the elongated shape; whereas, the aggregated UPy hard domains acted as the permanent physical cross-linkers and held the permanent shape.
  • Cryo-TEM analysis of the hydrogel shows that the UPy domains are spheres that are connected by the PEG chains to have an average distance of the UPy domains of 25 nanometer.
  • thermo-moisture responsive polyurethane SMP which is a glass transition adjusted SMP.
  • the present SMP is a crystallization
  • the UPy based supramolecular polymers are eminently suitable for producing bioactive materials owing to their low-temperature processability, favourable degradation and biocompatibility properties.
  • the present CEUPy polymer almost fulfils all the multi-dimensional requirements of SMPs and hydrogels used as biomaterials.
  • Amphiphilic copolymers containing biocompatible hydrophilic poly(ethylene glycol) (PEG) midsegments flanked with hydrophobic oligomeric methylene spacers and UPy end-caps capable of quadruple hydrogen bonding were previously prepared ( Figure 7, 1 ).
  • the telechelic polymers effectively gelled upon hydration, and showed remarkably dynamic gelation characteristics that depended largely on temperature and pH.
  • the intimately connected structural features and mechanical response are driven in part by the inherent thermodynamic incompatibility between the different chain segments in concert with the strong tendency for
  • polymer 1 will ultimately be molecularly dissolved at ambient temperature; dissolution is accelerated at elevated temperature.
  • a film consisting of polymer 2 does not dissolve molecularly in water at 25 °C; there was no measurable mass loss after soaking the films at concentration ⁇ 0.1 mg/mL for longer than 30 days.
  • the water is absorbed into the PEO domains, gradually dislodging increasing amounts of lattice-organized chain segments from crystalline regions with increasing water content, as evident from DSC ( Figure 8a). Eventually (ca. 42 wt % water), the material is essentially completely amorphous.
  • cryo-TEM micrographs reveal a nearly homogenous light matrix consisting of the amorphous hydrated PEO.
  • the hydrophobic segments effectively shield the water from disrupting the hydrogen bonding, upon which UPy dimerization depends.
  • the snapshot micrograph of the dry polymer is consistent with the fibrous structure attributed to PEO crystalline lamellae.
  • the white spots dispersed in a black matrix further corroborate the microphase separated hydrogel with hydrophobic spherical domains dispersed in a matrix of PEO-water.
  • This morphology must contain a large portion of bridged PEO segments connecting the dispersed hydrophobic compartments as a natural consequence of the molecular architecture.
  • the ramifications of this highly interpenetrating network are expressed partially by the remarkable stability of the hydrogel.
  • the suggested physical network would presumably have profound influence on the mechanical performance, and implicate that resilient materials should be realized in the hydrogel state. Furthermore, the performance of the materials and stability of the physical crosslinks in various temperature regimes is of great interest, both in the pristine and hydrated states.
  • Dynamic mechanical analysis shows a precipitous decrease (2 orders of magnitude) in both storage and loss moduli (E' and E", respectively) over a narrow temperature range of 50-60 °C for polymer 2 ( Figure 9a).
  • the indicated T tra ns corresponds well with T m p E o measured by DSC.
  • the transition occurs over a relatively narrow temperature range, which is typical of SMPs that employ semicrystalline switching domains.
  • the associated contributions to the mechanical response indicate predominantly elastic behavior (E'»E”) over the entire temperature range (20-140 °C).
  • the hydrophobic domains with strongly
  • Region I represents the linear viscoelastic regime, which is
  • the sample yields and begins to neck at approximately 10% strain, marked by a decrease in the stress resulting from smaller cross-sectional area than the original, undeformed guage (Region II).
  • the sample is subsequently cold drawn (Region III) as the neck propagates throughout the guage length, during which stress is essentially constant.
  • the strength continuously increases after the neck has completely propagated the guage, whereby the sample undergoes strain hardening with a remarkable stress increase (Region IV) until failure at -1000% strain (Point V).
  • the cumulative results from the tensile test suggest a remarkably tough material despite the relatively low UPy-hydrophobic content.
  • R (N) e max(N) - e res (N)
  • £ ma x(N) is the maximum strain for cycle N (i.e., 100% for each cycle) and £ r es(N) is taken as the point at which negligible stress was measured for the given cycle N.
  • the values for £ res are indicated on the inset of Figure 9c.
  • the remarkable resilience above T m, p E o is likely a direct consequence of the morphological features indicated by TEM.
  • Dogbone samples were cut from a film prepared by casting the polymer as a concentrated solution in methanol followed by extensive drying under high vacuum. The dry dogbone samples were then submerged in water for several days before performing the extension measurements. As with the elevated temperature measurements, the dogbones were subjected to uniaxial elongation to 100% strain followed by returning to the original position. Identical cycles were repeated five times, and the resilience was evaluated while measuring the forces associated with deformation (Figure 10a). The ultimate stress at 100% elongation was approximately 30* lower than the dry sample at ambient temperature, and 1 .5* lower than the dry sample at 70 °C.
  • Polymer 2 was formed into a permanent shape by two methods, which reflects the relative ease of processability.
  • the polymer was dissolved in methanol and cast as a film (ca. 0.5 mm thickness).
  • the polymer was pressed into a film at 120 °C using an aluminum mold and Teflon sheets for confinement. Either straight strips or curved "S" shapes were cut from the films, representing the permanent geometries.
  • the recovery was attributed solely to the thermal contribution; the mass of the sample was equal before and after the recovery experiment, and the polymer constituents are highly solvophobic for hydrocarbons like heptane. Submergence in liquid was used to aid in visualization of the very fast recovery process.
  • the CDI-activation was performed as described: the solid polymer was added in portions to a solution of 1 ,1 -carbonyldiimidazole (CDI; 2.8 g, 17.2 mmol) in chloroform. The mixture was stirred at 21 °C under an inert argon atmosphere for 8 h. Then the polymer was precipitated in an excess of diethylether. The product was instantly used for the next synthetic steps. Yield: 89%.
  • CDI activated PEG10k prepolymer (20.0 g, 5.0 mmol) was dissolved in 80 ml dry chloroform. To this solution 1 ,12-dodecyldiamine (6.41 g, 32.0 mmol) was added and the mixture was stirred under an argon atmosphere at room temperature for 48 h. After verification that conversion was complete by 1 H-NMR, 80 ml chloroform was added into the mixture and it was filtered. The filtrate was concentrated to around 50 ml and it was added dropwise into 800 ml diethyl ether under vigorous stirring. The white precipitate was collected, redissolved in 50 ml chloroform, filtered and the filtrate was precipitated again in 800 ml diethyl ether.
  • HDI-UPy-HDI was synthesized as described in the literature (Sontjens, S. H. M.; Renken, R. A. E.; van Gemert, G. M. L; Engels, T. A. P.; Bosman, A. W.; Janssen, H. M.; Govaert, L. E.; Baaijens, F. P. T. Macromolecules 2008, 41, 5703).
  • CEUPy polymer HDI-UPy-HDI 0.455 g in dry DMF (5 ml), was quickly added to a clear solution of DAPEG (10 g) in dry DMF (95 ml) with stirring at room temperature under N 2 atmosphere. After 30 min the reaction mixture was heated up to 75 °C for another 5 h, resulting in a clear viscous solution. The solution was precipitated in diethylene ether (1 .5 L), yielding a white power. The power was collected and dried at 40 °C under high vacuum. Yield: 98 %.
  • the chain-extended UPy hydrogelator is dissolved in methanol and by evaporation of the methanol the shape-memory material is formed.
  • the shape-memory material is formed.
  • the material can now be transformed in any other form by stretching at room temperature for thin specimens and by elevated temperature at 60-70 °C for thicker samples followed by cooling in the new form.
  • the old form is restored by subsequent heating (thermo-triggered shape memory) or by the swelling in water (water-triggered shape memory, by which a strong elastic hydrogel is formed with the form similar to the original sample when brought into contact with enough water.

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Abstract

Cette invention concerne un hydrogélifiant UPy à chaîne étendue (CEUPy) de conception récente qui est obtenu par ajout d'un composé organique hétérocyclique contenant un atome d'azote qui est substitué par au moins un groupe uréido à un poly(alkylène glycol), le groupe uréido et le poly(alkylène glycol) étant séparés par un espaceur hydrophobe. L'hydrogélifiant CEUPy obtenu forme un hydrogel supramoléculaire robuste et élastique à l'état hydraté ou gonflé, et présente des propriétés de mémoire de forme réagissant à la chaleur et à l'eau à l'état déshydraté.
PCT/EP2012/060841 2011-06-07 2012-06-07 Hydrogélifiant ayant des propriétés de mémoire de forme WO2012168392A1 (fr)

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CN104650333A (zh) * 2015-02-05 2015-05-27 浙江大学 聚乳酸/氢化聚丁二烯热塑性超分子弹性体及其制备方法
WO2017194786A1 (fr) * 2016-05-13 2017-11-16 Technische Universiteit Eindhoven Post-fonctionnalisation de matériaux supramoléculaires
CN107636049A (zh) * 2015-04-02 2018-01-26 密歇根大学董事会 自整合水凝胶及其制备方法
CN108822299A (zh) * 2018-06-26 2018-11-16 中国科学院长春应用化学研究所 羟氨基封端的聚乙二醇嵌段聚合物及制法和含该聚乙二醇嵌段聚合物的水凝胶及制法和应用
WO2019036378A1 (fr) * 2017-08-18 2019-02-21 The Regents Of The University Of California Adhésifs médicaux supramoléculaires bio-inspirés
US10329380B2 (en) 2017-05-17 2019-06-25 International Business Machines Corporation Lactide-derived polymers with improved materials properties via polyhexahydrotriazines (PHT) reaction
CN110048016A (zh) * 2019-03-26 2019-07-23 武汉华星光电半导体显示技术有限公司 薄膜封装结构、oled显示面板及其制作方法
CN110845743A (zh) * 2019-11-26 2020-02-28 上海大学 基于四重氢键的聚氨基酸基自愈合水凝胶及其制备方法
CN110922612A (zh) * 2019-12-02 2020-03-27 哈尔滨工程大学 一种离子型导电抗冻超分子水凝胶的制备方法
CN112877014A (zh) * 2021-01-19 2021-06-01 清华大学 一种环氧树脂热熔胶及其制备方法
CN114957535A (zh) * 2022-06-16 2022-08-30 西安石油大学 一种界面结合力可调控的粘合凝胶及其制备方法和应用
CN115011053A (zh) * 2022-06-21 2022-09-06 中国科学院苏州纳米技术与纳米仿生研究所 一种高反射分形结构水凝胶、其制备方法及应用

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CN104650333B (zh) * 2015-02-05 2016-08-24 浙江大学 聚乳酸/氢化聚丁二烯热塑性超分子弹性体及其制备方法
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