A strong and tough elastomer hybrid hydrogel and a preparation method thereof
Through a one-pot synthesis strategy, strong covalent bonds are formed at the interface between the elastomer and the hydrogel, which solves the problem of insufficient interfacial bonding strength and prepares hybrid hydrogels with excellent mechanical properties and biocompatibility, which are suitable for biomedicine, sensors, soft robots and other fields.
Patent Information
- Application Number
- CN202510094782.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-21
- Publication Date
- 2025-10-10
- Estimated Expiration
- 2045-01-21
AI Technical Summary
Existing technologies make it difficult to effectively integrate elastomers and hydrogels, resulting in insufficient interfacial bonding and uneven stress distribution, which affects the overall performance and long-term stability of the composite material, especially under external load or deformation conditions, limiting its effectiveness in high-load applications.
A one-pot synthesis strategy is adopted, in which an emulsion system is used to form a stable oil-in-water emulsion under the action of a surfactant. Free radical polymerization is initiated by light or heat stimulation to simultaneously construct an elastomer and hydrogel network, and strong covalent bonds are formed at the interface to achieve efficient integration of the elastomer and hydrogel.
The prepared strong and tough hybrid hydrogel has excellent mechanical properties and good biocompatibility, with a tensile strength of 0.1MPa-3.3MPa, an elongation at break of 3.2-22.5, an elastic modulus of 0.2MPa-1.9MPa, and a toughness of 0.5-15.0MJ/m3. It is suitable for industrial production and has adjustable transparency. It is widely used in the fields of biomedicine, sensors and soft robots.
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Figure CN119899309B_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of hydrogel materials, and in particular to a tough elastomer hybrid hydrogel and a preparation method thereof. Background Art
[0002] Soft materials, especially elastomers and hydrogels, have become a core component driving the development of modern technology and are widely used in fields such as tissue engineering, drug delivery, biomedical devices, microfluidics, optics, and soft robotics. Elastomers, due to their excellent mechanical strength, elasticity, and durability, play an important role in many applications that require both flexibility and strength. Hydrogels, with their excellent biocompatibility, low immunoreactivity, and softness, are ideal materials in the biomedical field, particularly suitable for contact with biological tissue or implantation applications. The advantages of elastomers and hydrogels complement each other. Therefore, the organic integration of the two to prepare a new hybrid material that combines the advantages of both has broad application prospects.
[0003] Combining the exceptional mechanical properties of elastomers with the excellent biocompatibility of hydrogels offers a novel strategy for designing novel soft materials. However, the physical and chemical differences between hydrophilic hydrogels and hydrophobic elastomers, particularly in terms of interfacial compatibility and performance matching, make seamless integration of the two challenging. Currently, most elastomer-hydrogel composites rely on a layered structure, where the hydrogel is adhered to an elastomer substrate. This design relies on complex surface engineering techniques to ensure a sufficiently strong interfacial bond between the hydrogel and elastomer. Specifically, the preparation of composites often requires surface modification of the substrate to enhance the interaction between the two materials and improve interfacial strength. Despite this, the significant difference in mechanical strength between the hydrogel and elastomer leads to uneven stress distribution at the interface, making cracks or interfacial failure more likely to occur, severely impacting the overall performance and long-term stability of the composite. This stress concentration problem is particularly pronounced under external loads or deformations, limiting the effectiveness of elastomer-hydrogel composites in certain high-load applications.
[0004] Currently, there are relatively few studies on macroscopically homogeneous elastomer-hydrogel composites. Huang et al. modified pre-synthesized elastomer microspheres by γ-ray irradiation technology, making them act as both initiators and cross-linkers during the composite process, thereby successfully achieving the grafting of hydrophilic chains. Recently, Tian et al. reported a new method that uses γ-rays to penetrate hydrophilic monomers into the hydrophobic network of elastomers, converting elastomers into hydrogels. Although these methods have made positive progress to a certain extent, their processes are complex and involve multiple steps, including pre-synthesis of elastomers, chemical modification, and interface functionalization, and often require the use of expensive equipment.
[0005] Therefore, with the growing demand for materials that combine the mechanical strength of elastomers with the biocompatibility and functionality of hydrogels, the development of efficient and simple integration strategies and preparation methods has become the key to current research. Summary of the Invention
[0006] The purpose of the present invention is to solve the above technical problems and provide a strong elastomer hybrid hydrogel and a preparation method thereof. The hydrogel prepared by this method has excellent mechanical properties and good biosafety.
[0007] The technical solution adopted by the present invention is as follows: a strong and tough elastomer hybrid hydrogel, comprising the following raw material components: an initiator, an elastomer monomer, an elastomer crosslinker, a water-soluble monomer, a water-soluble crosslinker, a surfactant, and water; the elastomer monomer is 1-90% of the total volume of the raw material components, the elastomer crosslinker is 0-100 mol% of the elastomer monomer; and the water-soluble crosslinker is 0-20 mol% of the water-soluble monomer.
[0008] Preferably, the initiator is 0.01-1 mol% of the elastomer monomer; the ratio of the mass of the water-soluble monomer to the volume of water is 1:2; the volume ratio of the elastomer monomer to water is 0.25-4:2; and the volume ratio of the surfactant to water is 0.05-0.1:1.
[0009] Preferably, the raw material components further include agar, and the concentration of agar in the raw material components is 10-50 mg / mL.
[0010] Preferably, the initiator is a free radical polymerization thermal initiator or a photoinitiator; the thermal initiator is one of dibenzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), potassium persulfate (KPS), and ammonium persulfate (APS); the photoinitiator is one of 1-hydroxycyclohexyl phenyl ketone, phenyl dimethoxyacetophenone, photoinitiator 2959, A-ketoglutaric acid, photoinitiator LAP, photoinitiator 819, photoinitiator TPO, and benzophenone (BP).
[0011] Preferably, the elastomer monomer is one of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-phenylethyl acrylate, isooctyl methacrylate, n-octyl acrylate, isooctyl acrylate, diethylaminoethyl methacrylate, vinyl propionate, methyl methacrylate, butyl methacrylate, hexyl methacrylate, and vinyl acetate.
[0012] Preferably, the elastomer crosslinking agent is one of ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, 1,13-tridecanediol dimethacrylate, p-vinylbenzene, and spiropyran.
[0013] Preferably, the water-soluble monomer is one of acrylamide, methacrylamide, N-(2-hydroxyethyl)acrylamide, N,N-dimethylacrylamide, N-acryloylglycinamide, acrylic acid, N-isopropylacrylamide, and hydroxyethyl methacrylate; and the water-soluble crosslinking agent is one of N,N'-methylenebisacrylamide, polyethylene glycol 600 diacrylate, and polyethylene glycol 1000 diacrylate.
[0014] More preferably, the surfactant is one of Tween 20, Tween 60, Tween 80, PVP, Span, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.
[0015] More preferably, the hydrogel has a tensile strength of 0.1 MPa-3.3 MPa, an elongation at break of 3.2-22.5, and an elastic modulus of 0.2 MPa-1.9 MPa.
[0016] The present invention also provides a method for preparing the tough elastomer hybrid hydrogel, comprising the following steps:
[0017] S1. Evenly mix an initiator, an elastomer crosslinking agent, and an elastomer monomer to prepare a solution A;
[0018] S2, uniformly mixing a water-soluble monomer, a water-soluble crosslinking agent and an aqueous solution containing a surfactant to prepare a solution B;
[0019] S3. Evenly mix solution A in S1 and solution B in S2 at a volume ratio of 0-1.3:1, inject into a mold, and initiate polymerization to obtain a strong elastomer hybrid hydrogel.
[0020] The beneficial effects of the present invention are:
[0021] 1) The present invention proposes a universal and efficient one-pot synthesis strategy for the preparation of tough elastomer cross-linked hybrid hydrogels. This method utilizes an emulsion system, an aqueous phase composed of a hydrogel prepolymer and an oil phase composed of an elastomer prepolymer, to form a stable oil-in-water emulsion under the action of a surfactant, and then utilizes external light or heat stimulation to initiate free radical polymerization of the elastomer and the hydrogel, thereby simultaneously constructing an elastomer and hydrogel network. And the interfacial copolymerization of the two is utilized to form a strong covalent bond between the two components, ensuring the overall homogeneity and stability of the hybrid material. Through this one-pot method, the elastomer and the hydrogel are efficiently integrated, and the hybrid material not only inherits the excellent mechanical strength of the elastomer, but also integrates the good biocompatibility and multifunctional properties of the hydrogel.
[0022] 2) The hydrogel prepared by the present invention has excellent mechanical properties, specifically: tensile strength range of 0.1MPa-3.3MPa, elongation at break range of 3.2-22.5, elastic modulus range of 0.2MPa-1.9MPa, toughness range of 0.5-15.0MJ / m 3 , high compression strength, adjustable range 17.9MPa-50.7MPa.
[0023] 3) The transparency of the hydrogel prepared by the present invention can be adjusted. The transparency of the hydrogel can be affected by adjusting the amount of elastomer cross-linking agent used (0% to 100 mol%, relative to the molar ratio of the elastomer monomer) and the elastomer ratio. Changes in the content of the elastomer cross-linking agent affect the degree of cross-linking of the hydrogel, thereby affecting the scattering and transmittance characteristics of light, achieving a smooth transition between transparent and opaque states; at the same time, by adjusting the proportion of elastomer monomer (1% to 90%), the transparency and structural properties of the hydrogel can be further optimized. Changes in the elastomer ratio have a significant impact on the macroscopic morphology and microstructure of the hydrogel, thereby allowing the transparency of the hydrogel to be finely adjusted between transparent and opaque.
[0024] 4) The hybrid hydrogel prepared by the present invention has the advantages of both the temperature responsiveness of elastomers and the good biocompatibility of hydrogels, and can be widely used in biomedicine, sensors, soft robots and other fields.
[0025] 5) The preparation method of the present invention is simple, easy to operate, and suitable for industrial large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 These are hydrogels of different shapes prepared by the mold in Example 1.
[0027] Figure 2 The circular hydrogel sheets prepared in Example 1 using different elastomer ratios are shown.
[0028] Figure 3These are circular hydrogel sheets prepared in Example 2 using different elastomer cross-linking agent contents.
[0029] Figure 4 The stress-strain comparison diagram of the hybrid hydrogels containing different elastomer ratios and the hydrogel control sample without elastomer in Example 1 is shown in FIG.
[0030] Figure 5 is the compressive stress-strain diagram of the hybrid hydrogel in Example 1.
[0031] Figure 6 This is a diagram of the temperature-responsive mechanical properties of the hybrid hydrogel in Example 1.
[0032] Figure 7 These are the live-dead staining results and cell survival rate of the hybrid hydrogel in Example 1. DETAILED DESCRIPTION
[0033] The present invention will be further described below with reference to the accompanying drawings and specific embodiments.
[0034] Example 1
[0035] Hybrid hydrogels (hydrogels with different elastomer ratios were prepared in this example) were prepared by the following steps:
[0036] (1) 10 mg of photoinitiator 819, 10 μL of elastomer crosslinker 1,6-hexanediol dimethacrylate, and 1 ml of elastomer monomer methyl acrylate were mixed to prepare solution A;
[0037] (2) 1 g of acrylamide and 2 mL of 1 vol% Tween 80 aqueous solution were manually shaken to mix thoroughly to prepare solution B;
[0038] (3) Solution A was mixed with solution B at 25 vol% of the total volume of solution A and solution B, vortexed for 5 min using a vortex disperser, and then injected into a glass mold with a 1 mm thick Teflon gasket using a syringe. After irradiation for more than 3 minutes, a hybrid hydrogel with an elastomer ratio of 25 vol% was obtained.
[0039] According to the above preparation method, solution A was mixed with solution B at 8 vol%, 14 vol%, 40 vol%, 50 vol%, and 57 vol% of the total volume of solution A and solution B to prepare hybrid hydrogels with elastomer ratios of 8 vol%, 14 vol%, 40 vol%, 50 vol%, and 57 vol%.
[0040] Table 1 shows the adjustable range of the hybrid hydrogel with an elastomer ratio of 8-57 vol% in Example 1, including elastic modulus E (MPa), breaking strength σ f(MPa), elongation at break and toughness W (MJ / m 3 ).
[0041] Table 1 Adjustable range of mechanical properties of hybrid hydrogels with elastomer ratio of 8-57 vol%
[0042]
[0043] Example 2
[0044] Hybrid hydrogels (hydrogels with different elastomer crosslinker ratios were prepared in this example) were prepared by the following steps:
[0045] (1) 10 mg of photoinitiator 819, 0.36 mol% (relative to MA) of elastomer crosslinker 1,6-hexanediol dimethacrylate, and 1 ml of elastomer monomer methyl acrylate were mixed to prepare solution A;
[0046] (2) 1 g of acrylamide and 2 mL of 1 vol% Tween 80 aqueous solution were manually shaken to mix thoroughly to prepare solution B;
[0047] (3) Solutions A and B were mixed together, vortexed for 5 min using a vortex disperser, and then injected into a glass mold with a 1 mm thick Teflon gasket using a syringe. After irradiation for more than 3 min, a hybrid hydrogel with an elastomer crosslinker dosage of 0.36 mol% (relative to MA) was obtained.
[0048] According to the above preparation method, the usage amount of the elastomer crosslinker 1,6-hexanediol dimethacrylate was adjusted to 0 mol%, 0.09 mol%, 0.18 mol%, 0.72 mol%, 1.08 mol%, and 1.44 mol% (relative to MA) to prepare hybrid hydrogels with elastomer ratios of 0 mol%, 0.09 mol%, 0.18 mol%, 0.72 mol%, 1.08 mol%, and 1.44 mol%.
[0049] Table 2 shows the adjustable range of the hybrid hydrogel with the elastomer crosslinker ratio of 0-1.44 mol% (relative to MA) in Example 2, including elastic modulus E (MPa), breaking strength σ f (MPa), elongation at break and toughness W (MJ / m 3 ).
[0050] Table 2 Adjustable range of hybrid hydrogels with elastomer ratio of 0-1.44 mol% (relative to MA)
[0051]
[0052] Example 3
[0053] Hybrid hydrogels (hydrogels with different hydrogel matrix cross-linker ratios were prepared in this example) were prepared by the following steps:
[0054] (1) Mix 10 mg of photoinitiator 819, 10 μl of 1,6-hexanediol dimethacrylate, and 1 ml of elastomer monomer methyl acrylate to prepare solution A;
[0055] (2) 1 g of acrylamide, 0.36 mol% (relative to AM) of the hydrogel matrix crosslinker N,N'-methylenebisacrylamide, and 2 mL of a 1 vol% Tween 80 aqueous solution were manually shaken and mixed to prepare solution B;
[0056] (3) Solutions A and B were mixed together, vortexed for 5 min using a vortex disperser, and then injected into a glass mold with a 1 mm thick Teflon gasket using a syringe. After irradiation for more than 3 min, a hybrid hydrogel with an elastomer crosslinker dosage of 0.36 mol% (relative to MA) was obtained.
[0057] According to the above preparation method, the usage amount of the hydrogel matrix crosslinker was adjusted to 0 mol%, 0.045 mol%, 0.18 mol% (relative to AM) to prepare hybrid hydrogels with hydrogel matrix crosslinker ratios of 0 mol%, 0.045 mol%, 0.18 mol%.
[0058] Table 3 shows the adjustable range of the hybrid hydrogel with the usage of 0-0.36 mol% (relative to MA) of the hydrogel matrix crosslinker in Example 3, including elastic modulus E (MPa), breaking strength σ f (MPa), elongation at break and toughness W (MJ / m 3 ).
[0059] Table 3 Adjustable range of hybrid hydrogels with a usage of 0-0.36 mol% (relative to AM) of hydrogel matrix crosslinker
[0060]
[0061] Example 4
[0062] Hybrid hydrogels (hydrogels with different agar contents were prepared in this example) were prepared by the following steps:
[0063] (1) 10 mg of photoinitiator 819, 10 μL of elastomer crosslinker 1,6-hexanediol dimethacrylate, and 1 ml of elastomer monomer methyl acrylate were mixed to prepare solution A;
[0064] (2) 40 mg, 80 mg, 120 mg, 160 mg, 200 mg agar were respectively dissolved with 1 g acrylamide and 2 mL 1 vol% Tween 80 aqueous solution at 90°C. Then mixed with solution A uniformly by vortex. Then injected into the mold, low temperature cooling to form the first network of agar. Illumination for more than 3 minutes to obtain agar concentration of 10 mg / ml, 20 mg / ml, 30 mg / ml, 40 mg / ml, 50 mg / ml double network hybrid hydrogel.
[0065] Table 4 is the adjustable range of agar double network hybrid hydrogel with agar concentration of 10-50 mg / mL in Example 4, including elastic modulus E (MPa), breaking strength σ f (MPa), breaking elongation and toughness W (MJ / m 3 ).
[0066] Table 4 is the adjustable range of agar double network hybrid hydrogel with agar concentration of 10-50 mg / mL
[0067]
[0068] Example 5
[0069] The hybrid hydrogel (agar double network hydrogel prepared by different elastomer crosslinking agents in this example) is prepared by the following steps:
[0070] (1) 10 mg of photoinitiator 819, 10 μL of elastomer crosslinking agent 1, 6-hexanediol dimethacrylate and 1 ml of elastomer monomer methyl acrylate are mixed uniformly to prepare solution A;
[0071] (2) 120 mg agar, 1 g acrylamide and 2 mL 1 vol% Tween 80 aqueous solution are dissolved at 90°C. Then mixed with solution A uniformly by vortex. Then injected into the mold, low temperature cooling to form the first network of agar. Illumination for more than 3 minutes to obtain agar double network hybrid hydrogel.
[0072] According to the above preparation method, the use amount of elastomer crosslinking agent 1, 6-hexanediol dimethacrylate is adjusted to 0.09 mol%, 0.18 mol%, 0.72 mol%, 1.44 mol% (relative to MA), and agar double network hybrid hydrogel with elastomer ratio of 0.09 mol%, 0.18 mol%, 0.72 mol%, 1.44 mol% is prepared.
[0073] Table 5 is the adjustable range of agar double network hybrid hydrogel with the use amount of elastomer crosslinking agent 1, 6-hexanediol dimethacrylate of 0-1.44 mol% (relative to MA) in Example 5, including elastic modulus E (MPa), breaking strength σ f(MPa), elongation at break and toughness W (MJ / m 3 ).
[0074] Table 5 Adjustable range of agar double network hybrid hydrogels with an elastomer crosslinker dosage of 0.09-1.44 mol% (relative to MA)
[0075]
[0076] In summary, the present invention comprises an emulsion mixed with a free radical polymerization initiator, an oil-soluble elastomer monomer and an elastomer crosslinker, a water-soluble hydrogel matrix monomer and a water-soluble hydrogel matrix crosslinker, a surfactant, and water. Free radical polymerization is initiated by light / heat, and a one-step copolymerization is performed to simultaneously form a network of elastomer and hydrogel, and a strong interface is formed between the two phases through covalent bonds, thereby synthesizing an elastomer hybrid hydrogel. The method is simple and highly operable. Easy to form: As needed, the elastomer can be transferred to a mold with a suitable structure to directly prepare a complex three-dimensional hydrogel shape with accurate details.
[0077] As attached Figure 1-7 As shown in the data in Tables 1-5, the hydrogel of the present invention has good controllability, and its performance can be significantly changed by adjusting the components slightly. For example, compared with the control sample, the mechanical properties are greatly improved by adding an elastomer, and the properties are continuously improved as the proportion of the elastomer increases. The present invention can adjust the raw material components and the ratio between them according to the specific application scenario to prepare hydrogel materials with different mechanical properties, intelligent responsiveness, and transparency, and has good application prospects in the fields of biomedicine, sensors, soft robots, etc.
[0078] The description and drawings of the present invention are considered to be illustrative rather than restrictive. On the basis of the present invention, those skilled in the art can make some substitutions and modifications to some of the technical features according to the disclosed technical content without creative work, and all of them are within the scope of protection of the present invention.
Claims
1. A tough elastomer hybrid hydrogel, characterized in that: The invention comprises the following raw material components: an initiator, an elastomer monomer, an elastomer crosslinking agent, a water-soluble monomer, a water-soluble crosslinking agent, a surfactant, and water; the elastomer monomer accounts for 1-90% of the total volume of the raw material components, the elastomer crosslinking agent accounts for 0-100 mol% of the elastomer monomer; the water-soluble crosslinking agent accounts for 0-20 mol% of the water-soluble monomer; The elastomer monomer is one of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-phenylethyl acrylate, isooctyl methacrylate, n-octyl acrylate, isooctyl acrylate, diethylaminoethyl methacrylate, vinyl propionate, methyl methacrylate, butyl methacrylate, hexyl methacrylate, and vinyl acetate; The elastomer crosslinking agent is one of ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, and 1,13-tridecanediol dimethacrylate; The water-soluble monomer is one of acrylamide, methacrylamide, N-(2-hydroxyethyl)acrylamide, N,N-dimethylacrylamide, N-acryloylglycinamide, acrylic acid, N-isopropylacrylamide, and hydroxyethyl methacrylate; the water-soluble crosslinking agent is one of N,N'-methylenebisacrylamide, polyethylene glycol 600 diacrylate, and polyethylene glycol 1000 diacrylate; The preparation method of the tough elastomer hybrid hydrogel comprises the following steps: S1. Evenly mix an initiator, an elastomer crosslinking agent, and an elastomer monomer to prepare a solution A; S2, uniformly mixing a water-soluble monomer, a water-soluble crosslinking agent and an aqueous solution containing a surfactant to prepare a solution B; S3. Evenly mix solution A in S1 and solution B in S2 at a volume ratio of 0-1.3:1, inject into a mold, and initiate polymerization to obtain a strong elastomer hybrid hydrogel.
2. A tough elastomer hybrid hydrogel according to claim 1, characterized in that: The initiator is 0.01-1 mol% of the elastomer monomer; the ratio of the mass of the water-soluble monomer to the volume of water is 1:2; the volume ratio of the elastomer monomer to water is 0.25-4:2; and the volume ratio of the surfactant to water is 0.05-0.1:
1.
3. The tough elastomer hybrid hydrogel according to claim 1, characterized in that: The raw material components further include agar, and the concentration of agar in the raw material components is 10-50 mg / mL.
4. The tough elastomer hybrid hydrogel according to claim 1, characterized in that: The initiator is a free radical polymerization thermal initiator or a photoinitiator; the thermal initiator is one of dibenzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), potassium persulfate (KPS), and ammonium persulfate (APS); the photoinitiator is one of 1-hydroxycyclohexyl phenyl ketone, phenyl dimethoxyacetophenone, photoinitiator 2959, A-ketoglutaric acid, photoinitiator LAP, photoinitiator 819, photoinitiator TPO, and benzophenone (BP).
5. The tough elastomer hybrid hydrogel according to claim 1, characterized in that: The surfactant is one of Tween 20, Tween 60, Tween 80, PVP, Span, sodium lauryl sulfate, and sodium dodecylbenzenesulfonate.
6. A tough elastomer hybrid hydrogel according to any one of claims 1 to 5, characterized in that: The hydrogel has a tensile strength of 0.1 MPa-3.3 MPa, an elongation at break of 3.2-22.5, and an elastic modulus of 0.2 MPa-1.9 MPa.