High internal phase emulsion, porous material with hierarchical communication structure and application

Abstract

The invention discloses a high-internal-phase emulsion, a porous material with a graded communicated pore structure and application, the high-internal-phase emulsion comprises an oil phase and a water phase, and the oil phase comprises a polymeric monomer, a crosslinking monomer, an emulsifier, an initiator and a polymer pore-foaming agent. According to the preparation method, the polymer pore-foaming agent is introduced into the high internal phase emulsion, and the polymer pore-foaming agent can form secondary pores in the porous material formed by curing the high internal phase emulsion in a dissolving manner, so that the finally obtained porous material has hierarchical structures with large-size pore diameters and small-size pore diameters at the same time; the porous material with the hierarchical structure is obtained.

Description

Technical Field

[0001] This invention belongs to the field of biomedical technology, specifically relating to a high internal phase emulsion and the porous materials with hierarchical interconnected pore structures obtained therefrom, and their applications. Background Technology

[0002] Porous materials formed after solidification of high internal phase emulsions possess a high porosity and highly interconnected pore structure, making them important materials for 3D cell culture scaffolds. However, the continuous phase of traditional high internal phase emulsion porous materials is mostly a dense structure, meaning its polymer backbone is a dense, non-porous, or low-porous structure. This means that material transport relies solely on the primary pore structure, which can easily lead to cell death within the scaffold due to nutrient deficiency and accumulation of metabolic waste, limiting its application in thick tissue block culture.

[0003] Meanwhile, in the fields of daily chemical hygiene products, existing porous materials also have significant limitations: for example, facial cleansing sponges, makeup remover pads and other products are mostly made of polyurethane foam, which has problems such as low porosity and poor liquid adsorption / release efficiency. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a high internal phase emulsion, a porous material with a hierarchical interconnected pore structure obtained therefrom, and its applications.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a high internal phase emulsion, the high internal phase emulsion comprising an oil phase and an aqueous phase, wherein the oil phase comprises polymeric monomers, crosslinking monomers, emulsifiers, initiators and polymeric porogens.

[0007] This invention introduces a polymeric porogen into a high internal phase emulsion. The polymeric porogen can form secondary pores in the porous material formed by the solidification of the high internal phase emulsion through dissolution. Therefore, the final porous material has a hierarchical structure with both large and small pore sizes, resulting in a porous material with a hierarchical structure.

[0008] Preferably, the HLB value of the polymeric porogen is 1-6, for example, 1, 2, 3, 4, 5, 6, etc.

[0009] Preferably, the polymeric porogen does not react with the polymeric monomer and the polymeric crosslinking agent.

[0010] Preferably, the solubility of the polymeric porogen in the porogen solvent is ≥1 g / 100mL, for example, 1 g / 100mL, 1.5 g / 100mL, 2 g / 100mL, 2.5 g / 100mL, 3 g / 100mL, 3.5 g / 100mL, 4 g / 100mL, 4.5 g / 100mL, 5 g / 100mL, 5.5 g / 100mL, etc.

[0011] Preferably, the pore-forming solvent includes an alkaline aqueous solution or an organic solvent, and more preferably, the alkaline aqueous solution includes an aqueous solution of NaOH, and the concentration of the aqueous solution of NaOH is 0.1-0.5 mol / L, such as 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, etc. The organic solvent includes ethanol, glycerol, or n-hexane, etc.

[0012] Preferably, the particle size D50 of the polymeric porogen is 1-50 μm, such as 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, etc.

[0013] The polymeric porogen provided by this invention needs to meet the following requirements:

[0014] i. The surface is hydrophobic, which avoids disrupting the "water-in-oil" emulsion structure; ii. Oil phase compatibility allows the polymeric porogen to be uniformly dispersed in the oil phase, avoiding agglomeration. It is also insoluble in the oil phase, exhibiting a predominantly particulate dispersion, and does not chemically react with polymeric monomers or crosslinking monomers, thus avoiding disruption of the "water-in-oil" emulsion structure; iii. Selective solubility allows it to dissolve in specific solvents without damaging the primary polymer backbone; iv. The particle size of the polymeric porogen is controllable.

[0015] Preferably, the polymeric porogen includes any one or a combination of at least two of polylactic acid, polycaprolactone, polybutylene succinate, polylactic acid-glycolic acid copolymer, or beeswax.

[0016] Preferably, the content of the polymeric porogen is 5-25% based on the total mass of the oil phase as 100%, for example, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, etc.

[0017] Preferably, the oil phase further includes a dispersing agent, and more preferably, the dispersing agent is butyl stearate.

[0018] Preferably, the amount of the dispersing agent added is 0.1-1% based on the total mass of the oil phase as 100%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc.

[0019] In this invention, the polymeric monomers, crosslinking monomers, emulsifiers, initiators, and aqueous phases in the high internal phase emulsion are all conventionally used components in high internal phase emulsions. This invention does not impose excessive limitations; it is sufficient to introduce polymeric porogens into the oil phase to meet application requirements. This invention only provides illustrative examples:

[0020] In this invention, the oil phase includes polymeric monomers, crosslinking monomers, emulsifiers, initiators, and polymeric porogens, which are exemplified herein:

[0021] Preferably, the polymeric monomer accounts for 5-97% of the weight of the oil phase, such as 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 97%, etc., and more preferably 40-80%. It may contain at least one water-insoluble monofunctional alkyl acrylate or alkyl methacrylate, vinyl monomer or biodegradable polymeric monomer.

[0022] Preferably, the functional alkyl acrylate or alkyl methacrylate includes C4-C18 alkyl acrylate and / or C2-C18 alkyl methacrylate.

[0023] Preferably, the vinyl monomers include styrene, vinyl chloride, vinylidene chloride, isoprene, and chloroprene, etc.

[0024] Preferably, the biodegradable polymeric monomers include PLA prepolymer (polylactic acid prepolymer), PCL prepolymer (polycaprolactone prepolymer), or PLGA prepolymer (polylactic acid-glycolic acid copolymer prepolymer).

[0025] Preferably, the crosslinking agent accounts for about 2-40% of the oil phase by weight, such as 2%, 5%, 10%, 20%, 30%, 40%, etc., and more preferably 2-30%; this type of crosslinking monomer includes any one or a combination of at least two of acrylate, methacrylate or divinylbenzene crosslinking agents containing two or more double bonds.

[0026] Preferably, the crosslinking agent is a multifunctional crosslinking monomer, including ethylene glycol dimethacrylate (EGDMA), hexanediol diacrylate (HDDA), polyethylene glycol diacrylate (PEGDA), trimethylolpropane trimethacrylate (TMPTA), divinylbenzene, etc.

[0027] Similarly, the present invention does not limit the amount or specific type of emulsifier; any HLB value that can meet the requirements of high internal phase emulsion is acceptable.

[0028] Preferably, the emulsifier includes any one or a combination of at least two of the following: Span 80, Span 60, polyglycerol ricinoleate, polyglycerol stearate, polyglycerol oleate, polyglycerol-3 stearate, polyglycerol-4 oleate, sucrose stearate, etc.

[0029] Preferably, the amount of emulsifier added is 1-20% of the mass of the oil phase, such as 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, etc.

[0030] Similarly, this invention does not limit the amount or specific type of initiator. Any initiator that can meet the requirements of high internal phase emulsion polymerization can be used in this invention. The initiator can be an oil-soluble initiator or a water-soluble initiator. Exemplary examples of this invention are listed below:

[0031] Preferably, the initiator is an oil-soluble initiator, and the amount of the oil-soluble initiator added is 0.05-10% of the mass of the oil phase, such as 0.05%, 1%, 2%, 5%, 10%, etc. The oil-soluble initiator includes peroxides, such as benzoyl peroxide, or amines, and azo compounds, such as azobisisobutyronitrile.

[0032] Preferably, the initiator is a water-soluble initiator, and the amount of the initiator can be 1-20% of the molar amount of the polymerizable monomer in the oil phase, such as 1%, 2%, 5%, 10%, 15%, 20%, etc., or 0.001-10% of the mass of the aqueous phase, such as 0.001%, 0.01%, 0.1%, 1%, 2%, 5%, 10%, etc.

[0033] The initiator of the present invention is preferably a thermal initiator, and preferably includes any one or a combination of at least two of benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), lauroyl peroxide (LPO), dicumyl peroxide (DCP), and tert-butyl peroxide (TBHP).

[0034] In this invention, the aqueous phase is also a conventional choice in the art, and this invention does not impose excessive limitations, but only provides an exemplary description:

[0035] In this invention, the aqueous phase includes deionized water and may also include water-soluble electrolytes. Introducing water-soluble electrolytes into the aqueous phase can reduce the solubility of oil phase components in water and maintain the structural stability of the water-in-oil system.

[0036] Preferably, the water-soluble electrolyte comprises chlorides or sulfates of alkaline earth metals (e.g., calcium or magnesium) or chlorides or sulfates of alkali metals (e.g., sodium).

[0037] Preferably, the amount of water-soluble electrolyte added is 0.2-40% based on the total mass of the aqueous phase as 100%, for example, 0.2%, 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, etc.

[0038] Preferably, the aqueous phase accounts for 75-97% of the total volume of the high internal phase emulsion, such as 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92%, 95%, 97%, etc.

[0039] In this invention, the method for preparing the high internal phase emulsion includes:

[0040] (1) The polymeric porogen is mixed with the emulsifier, and then mixed with the polymeric monomer, crosslinking monomer and initiator to obtain an oil phase mixture;

[0041] (2) Add the aqueous phase dropwise to the oil phase, and continue stirring after the addition is complete to obtain the high internal phase emulsion.

[0042] In a second aspect, the present invention provides a porous material with a hierarchical interconnected pore structure, which is prepared from the high internal phase emulsion described in the first aspect.

[0043] The porous material provided by this invention is prepared by first solidifying a primary pore structure framework and then dissolving a polymeric porogen to prepare a secondary microporous structure, thereby obtaining a porous material with a hierarchical interconnected pore structure. Specifically, in the solidification stage, only the polymerizable monomers in the oil phase undergo polymerization to form a primary pore framework containing a soluble polymeric porogen. The polymeric porogen remains "inert" at this stage and does not participate in the reaction. After the framework is solidified, the polymeric porogen is selectively dissolved using a specific solvent. After the porogen dissolves, it leaves uniformly sized and well-connected secondary micropores inside the framework, with virtually no impact on the primary pore framework. Therefore, the porous material provided by this invention has a hierarchical interconnected structure and excellent mechanical properties.

[0044] Moreover, the secondary micropore size and connectivity of the porous material obtained by this invention can be controlled by the particle size and amount of polymeric porogen, thus achieving "controllable structural parameters".

[0045] In the porous material provided by this invention, the pore size of the primary pore framework is 30-500 μm, such as 30 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, preferably 40-120 μm, such as 40 μm, 50 μm, 60 μm, 80 μm, 100 μm, 120 μm, etc., with a connectivity ≥85%, such as 85%, 86%, 88%, 90%, 92%, etc., and a pore wall thickness of 5-20 μm, such as 5 μm, 8 μm, 10 μm, 12 μm. The pore sizes of the secondary micropores are 1-50 μm, such as 1μm, 2μm, 5μm, 8μm, 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm, 50μm, etc., preferably 5-30μm, such as 5μm, 10μm, 15μm, 20μm, 25μm, 30μm, etc., and the porosity is 30-60%, such as 30%, 35%, 40%, 45%, 50%, 55%, 60%, etc.

[0046] The porous material provided in this invention has a compressive modulus of 0.5-5 MPa and exhibits excellent mechanical properties.

[0047] Thirdly, the present invention provides a method for preparing a porous material with a hierarchical interconnected pore structure as described in the second aspect, the method comprising:

[0048] The high internal phase emulsion described in the first aspect is subjected to a curing reaction. After the curing reaction is completed, the polymeric porogen is removed using a porogenizing solvent, and the material is dried to obtain the porous material with a hierarchical interconnected pore structure.

[0049] The preparation method provided by this invention achieves complete separation of polymerization and pore formation, and the size of the secondary micropore structure in the obtained porous material is controllable without damaging the primary framework structure. At the same time, the preparation method has high process controllability and the obtained porous material has strong structural stability, which can fully meet the needs of scaffold materials in fields such as 3D cell culture and tissue engineering.

[0050] Preferably, the curing reaction includes thermocuring and / or photocuring.

[0051] Preferably, the temperature for heat curing is 60-100℃, such as 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, etc., and the time is 0.5-8h, such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, etc.

[0052] Preferably, the pore-forming solvent is an aqueous solution of NaOH (for biodegradable polymers such as polylactic acid, PLGA, and PCL), and the concentration of the NaOH aqueous solution is preferably 0.1-0.5 mol / L, such as 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, etc.; if the pore-forming agent is beeswax, the solvent can be n-hexane.

[0053] Preferably, the method for removing polymeric porogens using solvents includes an immersion method, immersing the porous material until the mass of the porous material is constant.

[0054] Preferably, the drying method includes vacuum drying or freeze drying. Optionally, purification is performed after the polymerization reaction to remove unreacted monomers and residual salts.

[0055] Fourthly, the present invention provides the application of the high internal phase emulsion as described in the first aspect or the porous material with a hierarchical interconnected pore structure as described in the second aspect in cell culture and daily chemical hygiene products.

[0056] The porous material provided by this invention has a hierarchical structure that combines "large-size cell growth scaffold" and "small-size material transport channel", which can fully meet the application requirements of scaffold materials.

[0057] The porous material provided by this invention can be used in the field of sanitary napkins, dressings and other daily chemical hygiene products. One or more layers of porous material with the same or different pore sizes can be used as the core of sanitary napkins, dressings and other daily chemical hygiene products. Through its high porosity, high connectivity and controllable pore size, it can absorb, guide, lock water, prevent backflow or slow release liquids such as water, menstrual blood, blood, body fluids, and nutrients, so that the products have excellent properties such as thinness, dryness, long-lasting effect and slow release.

[0058] The porous material with a hierarchical interconnected pore structure provided by this invention has the following advantages:

[0059] (1) Achieving “complete separation of polymerization solidification and micropore preparation”: This invention avoids interference from the pore-forming agent on the polymerization of the skeleton in the synchronous preparation process by “dissolving and leaching out” soluble particles after the skeleton is solidified, thereby reducing the collapse rate of secondary micropores;

[0060] (2) Controllable structure: The porous material provided by the present invention has a primary macropore with pore size and porosity that are precisely controlled by the high internal phase emulsion template method, and a secondary micropore with pore size that is directly determined by the particle size of soluble particles, and porosity that is controlled by the amount of particles added, thus achieving a hierarchical porous structure with controllable structure.

[0061] (3) Performance balance between cell connectivity and strength: The primary skeleton in the porous material provided by the present invention is first solidified and then secondary micropores are prepared to avoid damage to the skeleton during the pore-forming process, ensure the physical strength of the material, and at the same time maintain high connectivity and high material transport efficiency. Attached Figure Description

[0062] Figure 1 This is a SEM image of the cross-section of the porous material obtained in Example 1 of the present invention. Detailed Implementation

[0063] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0064] Unless otherwise specified, the raw materials involved in the following specific embodiments of the present invention are all conventional materials in the art, and can be purchased from commercially available products. Some raw material information is as follows:

[0065] PLGA prepolymer: Sigma-Aldrich, model 75 / 25;

[0066] PLA ultrafine particles: Aladdin, with particle sizes D50 of 0.5 μm, 1 μm, 10 μm, 50 μm, and 60 μm (HLB value 2.5, difference from PLGA solubility parameter 2.2).

[0067] PCL particles: NatureWorks, particle size D50=20 μm (HLB value 3.0);

[0068] PBS particles: Maclean, particle size D50=15 μm (HLB value 2.8);

[0069] EGDMA, TMPTA: Maclean's, 98% purity;

[0070] Span 80: Walter, UK;

[0071] Beeswax: purchased from Maclean, B766562, particle size D50=20 μm (obtained by sieving).

[0072] Example 1

[0073] This embodiment provides a high internal phase emulsion and a porous material with a hierarchical interconnected pore structure, as follows:

[0074] (1) High internal phase emulsion, composed of an oil phase and an aqueous phase, as follows:

[0075] Oil phase: 60 parts PLGA prepolymer, 15 parts EGDMA, 15 parts PLA ultrafine particles, 4 parts AIBN, 6 parts Span 80;

[0076] Aqueous phase: deionized water + 5 wt% calcium chloride, oil phase to aqueous phase mass ratio is 1:5;

[0077] The preparation method is as follows: PLA ultrafine particles are mixed with Span 80 and stirred at 800 rpm for 15 min. Then, PLGA prepolymer, EGDMA and AIBN are added and stirred at 500 rpm for 30 min to form a transparent "oil phase-particle mixture". Under stirring at 500 rpm, the aqueous phase is added dropwise to the oil phase at 5 mL / s and then stirred for 15 min to form a stable high internal phase emulsion.

[0078] (2) Preparation of porous materials:

[0079] The high internal phase emulsion was injected into a polytetrafluoroethylene mold (5cm×5cm×0.5cm) and placed in an oven for heating and curing at 90℃ for 2 hours to ensure complete polymerization and obtain a stable primary cell structure.

[0080] The material was soaked in 0.3 mol / L NaOH aqueous solution at 37°C with shaking for 8 hours, the solution was changed 3 times, and the material was washed 5 times with deionized water. Then it was vacuum dried at 35°C for 12 hours to obtain a porous material with a hierarchical interconnected pore structure.

[0081] Example 2

[0082] This embodiment provides a high internal phase emulsion and a porous material with a hierarchical interconnected pore structure.

[0083] The difference from Example 1 is that in this example, PLA ultrafine particles are replaced with PCL particles.

[0084] Examples 3-6

[0085] This embodiment provides a high internal phase emulsion and a porous material with a hierarchical interconnected pore structure.

[0086] The difference from Example 1 is that in this example, by adjusting the amount of PLA ultrafine particles added, the mass percentage of PLA ultrafine particles in the oil phase is 5% (Example 3), 25% (Example 4), 2% (Example 5), and 28% (Example 6).

[0087] Examples 7-10

[0088] This embodiment provides a high internal phase emulsion and a porous material with a hierarchical interconnected pore structure.

[0089] The difference from Example 1 is that in this example, the particle size of PLA ultrafine particles is 1 μm (Example 7), 50 μm (Example 8), 0.5 μm (Example 9), and 60 μm (Example 10).

[0090] Example 11

[0091] This embodiment provides a high internal phase emulsion and a porous material with a hierarchical interconnected pore structure.

[0092] (1) High internal phase emulsion, composed of an oil phase and an aqueous phase, as follows:

[0093] Oil phase: 65 parts PLGA prepolymer, 12 parts EGDMA, 15 parts PBS particles, 3 parts AIBN, 5 parts Span 80, 0.5 parts butyl stearate;

[0094] Aqueous phase: deionized water + 5 wt% calcium chloride, with a mass ratio of oil phase to aqueous phase of 1:3;

[0095] The preparation method is the same as in Example 1.

[0096] (2) Preparation of porous materials:

[0097] The high internal phase emulsion was injected into a polytetrafluoroethylene mold (5cm×5cm×0.5cm) and placed in an oven for heating and curing at 60℃ for 8 hours to ensure complete polymerization and obtain a stable primary cell structure.

[0098] The material was soaked in 0.1 mol / L NaOH aqueous solution at 37°C with shaking for 24 h, the solution was changed 3 times, and the material was washed 5 times with deionized water. Then it was vacuum dried at 35°C for 12 h to obtain a porous material with a hierarchical interconnected pore structure.

[0099] Example 12

[0100] This embodiment provides a high internal phase emulsion and a porous material with a hierarchical interconnected pore structure.

[0101] (1) High internal phase emulsion, composed of an oil phase and an aqueous phase, as follows:

[0102] Oil phase: 55 parts butyl acrylate, 13 parts TMPTA, 20 parts beeswax, 4 parts BPO, 8 parts polyglycerol ricinoleate, 0.8 parts butyl stearate;

[0103] Aqueous phase: deionized water + 5 wt% calcium chloride, with a mass ratio of oil phase to aqueous phase of 1:8;

[0104] The preparation method is the same as in Example 1.

[0105] (2) Preparation of porous materials:

[0106] The high internal phase emulsion was injected into a polytetrafluoroethylene mold (5cm×5cm×0.5cm) and placed in an oven for heating and curing at 100℃ for 0.5 h to ensure complete polymerization and obtain a stable primary cell structure.

[0107] The material was soaked in hexane at 37°C with shaking for 6 hours, the solution was changed 3 times, and the material was washed 5 times with deionized water. Then it was vacuum dried at 35°C for 12 hours to obtain a porous material with a hierarchical interconnected pore structure.

[0108] Comparative Example 1

[0109] This comparative example provides a high internal phase emulsion and a porous material.

[0110] The difference from Example 1 is that no PLA ultrafine particles were added in this comparative example.

[0111] Comparative Examples 2-3

[0112] This comparative example provides a high internal phase emulsion and a porous material.

[0113] The difference from Example 1 is that, in this comparative example, PLA ultrafine particles were replaced with NaCl (Comparative Example 2) and toluene (Comparative Example 3).

[0114] Performance testing

[0115] The performance of the samples provided in the examples and comparative examples was tested using the following methods:

[0116] (1) Cell structure: The pore structure was observed using a scanning electron microscope (SEM, TESCANMIRA3). The diameters of 50 primary pores and 100 secondary pores were randomly measured (the difference between the maximum and minimum diameters was ≤10, which was considered to be a relatively uniform pore size distribution, and the average diameter could be calculated). The connectivity rate was calculated as (number of connected pores / total number of pores × 100%).

[0117] Figure 1 The image shows a cross-sectional SEM image of the porous material obtained in Embodiment 1 of the present invention. As can be seen from the image, the porous material provided by the present invention has a hierarchical structure that combines large-sized pores and small-sized pores.

[0118] (2) Mechanical strength: universal testing machine (Instron5967), sample size 10mm×10mm×5mm, compression rate 1mm / min, and the stress at 8% strain is taken as the compressive modulus;

[0119] (3) Biocompatibility: Inoculation with BMSCs (1×10 5 Cells were cultured for 7 days (cells / mL) and cell viability was tested using the CCK-8 assay.

[0120] (4) Material transport efficiency: FITC fluorescent probe (1 mg / mL, dimethyl sulfoxide as solvent) was dropped onto the material surface (thickness 5 mm), and the diffusion distance within 2 h was observed by confocal microscopy to calculate the transport rate (μm / h).

[0121] The test results are shown in Table 1:

[0122] Table 1

[0123]

[0124] Note: The pore size uniformity of the secondary pores in Comparative Example 3 is extremely poor, with the pore diameter randomly distributed in the range of 10-30 μm.

[0125] As can be seen from the examples and performance tests, the porous material provided by the present invention includes secondary pores formed by polymeric porogens and primary pores formed by high internal phase emulsions. That is, the porous material provided by the present invention has a hierarchical structure with both large and small pore sizes.

[0126] The comparison between Example 1 and Example 2 shows that the PCL porogen has a slightly higher rigidity, resulting in a higher compressive modulus of 1.3 MPa. The secondary pore size increases to 20 μm due to the increased particle size, and the mass transport rate increases to 88 μm / h. This demonstrates that different polymer porogens can be adapted to different mechanical and transport requirements.

[0127] As can be seen from the comparison between Examples 1 and Examples 3-6, in this invention, as the amount of pore-forming agent added increases, the secondary pore porosity increases from 30% to 60%, the compressive modulus decreases from 1.5 MPa to 0.8 MPa, and the mass transport rate increases from 72 μm / h to 95 μm / h, demonstrating a controllable correlation between "addition amount - porosity - performance".

[0128] As can be seen from the comparison between Examples 1 and Examples 7-10, in this invention, the particle size of the porogen is directly matched with the pore size of the secondary pores. At the same time, the mass transport rate increases with the increase of particle size (from 65 μm / h to 90 μm / h), proving that particle size is the core control parameter of secondary pore size.

[0129] As can be seen from the comparison of Examples 1-12, when the porous material provided by the present invention is used for cell culture, the cell survival rate is ≥91% and the material transport rate is ≥65 μm / h, which is significantly better than Comparative Example 1 without porogen (survival rate 80%, transport rate 35 μm / h) and Comparative Example 2 without inorganic porogen (survival rate 85%, transport rate 42 μm / h), proving the core value of polymer porogens.

[0130] The present invention has been illustrated through the above embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials used in the present invention, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A high internal phase emulsion, characterized in that, The high internal phase emulsion comprises an oil phase and an aqueous phase, wherein the oil phase comprises polymeric monomers, crosslinking monomers, emulsifiers, initiators, and polymeric porogens.

2. The high internal phase emulsion according to claim 1, characterized in that, The HLB value of the polymeric porogen is 1-6; And / or, the polymeric porogen does not react with the polymeric monomer and the polymeric crosslinking agent; And / or, the solubility of the polymeric porogen in the porogen solvent is ≥1 g / 100 mL, preferably the porogen solvent includes an aqueous solution of NaOH or n-hexane, and more preferably the concentration of the aqueous solution of NaOH is 0.1-0.5 mol / L; And / or, the particle size D50 of the polymeric porogen is 1-50 μm.

3. The high internal phase emulsion according to claim 1 or 2, characterized in that, The polymeric porogen includes any one or a combination of at least two of polylactic acid, polycaprolactone, polybutylene succinate, polylactic acid-glycolic acid copolymer, or beeswax.

4. The high internal phase emulsion according to any one of claims 1-3, characterized in that, The content of the polymeric porogen is 5-25% based on the total mass of the oil phase (100%).

5. The high internal phase emulsion according to any one of claims 1-4, characterized in that, The oil phase also includes dispersing agents.

6. A porous material with a hierarchical interconnected pore structure, characterized in that, It is prepared from the high internal phase emulsion according to any one of claims 1-5.

7. A method for preparing a porous material with a hierarchical interconnected pore structure as described in claim 6, characterized in that, The preparation method includes: The high internal phase emulsion of any one of claims 1-5 is subjected to a curing reaction. After the curing reaction is completed, the polymeric porogen is removed using a porogenizing solvent, and the material is dried to obtain the porous material with a hierarchical interconnected pore structure.

8. The preparation method according to claim 7, characterized in that, The curing reaction includes thermocuring and / or photocuring; Preferably, the thermosetting temperature is 60-100℃ and the time is 0.5-8h.

9. The preparation method according to claim 7 or 8, characterized in that, The pore-forming solvent is an aqueous solution of NaOH or n-hexane, and more preferably, the concentration of the aqueous solution of NaOH is 0.1-0.5 mol / L.

10. The application of a high internal phase emulsion as described in any one of claims 1-5 or a porous material with a hierarchical interconnected pore structure as described in claim 6 in cell culture and daily chemical hygiene products.

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