CN117487238A - Method for producing porous material, and method for adjusting pore structure of porous material - Google Patents

Abstract

The present invention relates to a method for producing a porous material, and a method for adjusting the pore structure of a porous material. The method for producing a porous material of the present invention comprises: a) Mixing a monomer composition comprising a lipophilic monomer and Janus particles, wherein the surface of the Janus particles is provided with a hydrophilic part and a hydrophobic part, and the hydrophilic part comprises polysiloxane with specific hydrophilic groups; b) Adding an aqueous medium to the mixture obtained in step a) and emulsifying under dynamic action to form an emulsified composition, wherein the monomer composition is as a continuous phase and the aqueous medium is as a dispersed phase; c) The emulsified composition is subjected to a polymerization reaction. The porous material of the present invention comprises a polymer base material and pores therein, wherein the Janus particles are contained at the inner wall of the pores, and the diameter of the pores is more than 1 μm. In addition, the conditioning method of the present invention is achieved by utilizing the above Janus particles in the preparation of the porous material.

Description

Method for manufacturing porous materials and methods of porous materials and pore structures of porous materials Adjustment method

Technical field

The present invention relates to a method for manufacturing a porous material and a method for adjusting the porous material and the pore structure of the porous material.

Background technique

The mechanical and thermal properties and high specific surface area brought by the porous structure provide a broad range of applications for porous materials. For example, polymer porous materials are used in fields such as shock absorption, sound absorption, heat insulation, catalysis, and separation.

According to the different porogenic principles of porous materials, the preparation methods of porous materials can be roughly divided into: physical porogen (porogen phase into pores), chemical porogen (reaction to generate porogen), template method porogen (porogen in advance) Constructing porous templates), etc. Among the preparation methods of porous materials, physical pores and chemical pores are fast in preparation and have large preparation quantities. However, the pore structure usually lacks fine control and is difficult to control. Template-induced pores are based on pre-constructed templates, which can finely control the pore structure in many aspects, giving porous materials richer properties and broader applications.

For polymeric porous materials, the high internal phase emulsion template method (also known as the concentrated emulsion template method) has received widespread attention. Generally, high internal phase emulsions generally refer to emulsions with an internal phase volume fraction exceeding 74%. However, Menner et al. also proposed that emulsion templates that can produce open-pore materials (regardless of the internal phase volume fraction) should be classified as "high internal phase emulsions". Therefore, in the present invention, the term "high internal phase emulsion template method" or "high internal phase emulsion method" is used to refer to the emulsion template method for preparing porous materials, so as to be different from the emulsion polymerization or emulsion template used in other materials fields. Dharma distinction. In the high internal phase emulsion method, porous materials can be obtained by fixing the continuous phase (such as polymerization and other processes) and then removing the internal dispersed phase.

In order to obtain a stable high internal phase emulsion, it is necessary to select the appropriate type and dosage of surfactants. Usually, lipophilic small molecule surfactants such as Span 80 can be used. However, the method of using small molecule surfactants usually has the following problems: (1) In order to stabilize the emulsion and obtain good porosity, the dosage of surfactant is high. For example, sometimes the dosage reaches about 20wt% to obtain the porosity. Higher porous materials; (2) A complex and cumbersome washing process is required to remove surfactants, and it is difficult to completely remove. In other functional application scenarios, although surfactants can provide functional sites, they There is also the problem that small molecules are easy to migrate and lose.

In addition to small molecule surfactants, research in this field has also been proposed on using nanoparticles with uniform surface properties as emulsion stabilizers to prepare water-in-oil high internal phase emulsions. Thanks to the pickering effect, these particles have high interfacial desorption energy after being adsorbed to the water-oil interface and can anchor to the interface and thus stabilize the emulsion. However, due to the protective effect of these particle layers on the internal phase droplets, when manufacturing materials with through-hole structures, it is usually difficult to form a good through-hole structure, and surfactants are required to increase the porosity. In addition, amphiphilic polymers with block structures or block polymers with more complex topological structures and their self-assembled colloidal particles have also received certain attention in the field of stable high internal phase emulsions. However, the manufacture of macromolecular emulsifiers or self-assembled colloidal particles based on block copolymers involves a complex, tedious, and demanding block copolymerization process with low yields and difficulty in large-scale promotion.

Janus particles, as a new type of material, have attracted widespread attention due to their unique structure and performance and their wide range of application prospects. Usually Janus particles have two partitions with different structures, morphologies or compositions, such as having both a hydrophilic part and a lipophilic part. This property allows Janus particles to be used as solid emulsifiers.

Recently, it was proposed to prepare amphiphilic tadpole-like Janus nanoparticles (composed of linear poly(methyl methacrylate) “tails” and cross-linked poly(4-vinylpyridine) through intramolecular cross-linking of block copolymers). "head" composition), and use it as a stabilizer for high internal phase emulsion to prepare high internal phase emulsion and porous materials, the pore structure of which can be adjusted within a certain range (Non-patent Document 1). However, the Janus particles used in this work were made by intramolecular cross-linking of block copolymers, and this method is currently not conducive to large-scale preparation of particles.

In addition, it is also proposed in the prior art to prepare snowman-shaped silica/linear polystyrene Janus particles and modify one end of the silica with ionic liquid or n-octyl group to obtain the particles, and then use the particles to prepare Polymer porous material having a through-hole structure (Patent Documents 1 and 2).

However, the n-octane modification in Patent Document 1 is to adjust the hydrophilic-lipophilic balance of Janus particles to obtain a stable water-in-oil emulsion when styrene and divinylbenzene are used as the forming monomers of the porous material, but However, the hydrophilic groups of the Janus particles themselves are damaged, thereby damaging the good interfacial activity. In addition, the performance of particles obtained by n-octane modification is actually more inclined to nanoparticles with uniform surface properties. The ability to adjust the pore structure of the obtained polymer porous material is still insufficient, especially the through-hole structure still has defects. Case.

In addition, the ionic liquid modification technical solution given in Patent Document 2 relies on a two-step process of imidazole siloxane modification and haloalkyl ionization. The modification process is complex, especially the second step operation relies heavily on the interaction between haloalkyl and imidazole groups. The salt-forming process will produce corrosive free halide ions, which is not conducive to industrial production and may cause environmental pollution. In addition, the ionic liquid modified group has the characteristics of easy salt-forming, making the material extremely easy to absorb water, which is not conducive to practical applications.

In addition, most of the porous materials currently obtained by the high internal phase emulsion method use styrenic monomers and cross-linking agents as the continuous phase (for example, the types of applicable monomers in Patent Documents 1 and 2 are very limited, and are limited to (Copolymerization of styrene and divinylbenzene), the continuous phase polymer obtained after polymerization has a high glass transition temperature, is hard and brittle, and is easily pulverized. However, there is little research on the feasibility of using the high internal phase emulsion method to obtain other polymer materials in the existing technology, which limits the industrial application of the high internal phase emulsion method to prepare porous materials with various properties.

Therefore, in the existing technology, it is easy to obtain porous materials with various pore structures and can be made from various polymer materials and can provide abundant and stable functional expansion sites, which are simple to operate and easy to promote in industry. There is still a need for manufacturing methods of materials.

non-patent literature

Non-patent document 1: Macrocellular polymer foams from water in oil highinternal phase emulsion stabilized solely by polymer Janus nanoparticles: preparation and their application as support for Pd catalyst, Fangyuan Yi et al., RSC Adv., 2015, 5, 40227

patent documents

Patent document 1: CN106519099A

Patent document 2: CN106496395A

Contents of the invention

Invent the problem to be solved

In view of the above-mentioned deficiencies in this field, the technical problem to be solved by the present invention is to provide a method that can easily obtain adjustable pore structure and performance at low cost through a high internal phase emulsion method and can provide rich and stable functional expansion. A method for manufacturing porous materials with simple operation and excellent environmental friendliness.

The technical problem to be solved by the present invention is to provide a porous material with adjustable pore structure and adjustable performance and which can provide abundant and stable functional expansion sites.

The technical problem to be solved by the present invention is to provide a method that can easily adjust the pore structure of porous materials at low cost in a high internal phase emulsion method, is simple to operate, and has excellent environmental friendliness.

solutions to problems

According to the intensive research of the inventor of the present invention, it is found that the above technical problems can be solved through the implementation of the following technical solutions:

[1]. A method of manufacturing porous materials, which includes:

a) mixing a monomer composition including a lipophilic monomer and Janus particles, wherein the surface of the Janus particles is provided with a hydrophilic part and a hydrophobic part, and the hydrophilic part includes a polysiloxane having a hydrophilic group, The hydrophilic group is at least one selected from the group consisting of amino group, hydroxyl group, ether group, amide group, carboxyl group and its anhydride group, sulfonic acid group, sulfinic acid, phosphate group, phosphite group, and phosphine phosphate group;

b) Add an aqueous medium to the mixture obtained in step a) and emulsify it under dynamic action to form an emulsified composition, wherein in the emulsified composition, the monomer composition serves as a continuous phase, and the aqueous medium as a dispersed phase;

c) subjecting the emulsified composition to polymerization reaction.

[2]. The manufacturing method according to [1], wherein in step a), the lipophilic monomer is at least one selected from the group consisting of styrenic monomers and (meth)acrylate monomers. .

[3]. The manufacturing method according to [1] or [2], wherein in step a), the Janus particles are in the shape of a snowman, and the size of the Janus particles is 250 to 1000 nm; among the Janus particles, The hydrophobic portion includes a hydrophobic polymer.

[4]. The manufacturing method according to any one of [1] to [3], wherein in step a), the amount of Janus particles is 0.01 to 0.01 based on the total mass of the monomer composition. 50% by mass; in step a), surfactants other than the Janus particles may not be used.

[5]. The manufacturing method according to any one of [1] to [4], wherein in step b), in the emulsified composition, the proportion of the monomer composition is 10 to 10 based on volume conversion. 95%.

[6]. The manufacturing method according to any one of [1] to [5], wherein in step b), the aqueous medium is added in batches.

[7]. The manufacturing method according to [6], wherein in step b), the emulsification time between two additions is 10 seconds to 15 minutes.

[8]. The manufacturing method according to any one of [1] to [7], wherein in step c), the polymerization temperature is 50 to 100°C and the polymerization time is 7 to 48 hours.

[9]. A porous material, which includes a polymer substrate and pores distributed therein. The inner wall of the pores includes Janus particles. The surface of the Janus particles is equipped with a hydrophilic part and a hydrophobic part. The hydrophilic part contains Polysiloxane with hydrophilic groups, the hydrophilic groups being selected from the group consisting of amino groups, hydroxyl groups, ether groups, amide groups, carboxyl groups and their anhydride groups, sulfonic acid groups, sulfinic acid, phosphate groups, sub-groups At least one of a phosphate group and a phosphine phosphate group has a pore diameter of 1 μm or more.

[10]. The porous material according to [9], wherein the monomer forming the polymer base material is at least one selected from the group consisting of styrene-based monomers and (meth)acrylate-based monomers.

[11]. The porous material according to [9] or [10], wherein the Janus particles are in the shape of a snowman, and the size of the Janus particles is 250 to 1000 nm.

[12]. The porous material according to any one of [9] to [11], wherein the porous material has an open cell structure, and the porosity in the open cell structure is 0.1 to 30%, The diameter of the hole window is 1~500μm.

[13]. A method for adjusting the pore structure of porous materials, which includes:

a) mixing a monomer composition including a lipophilic monomer and Janus particles, wherein the surface of the Janus particles is provided with a hydrophilic part and a hydrophobic part, and the hydrophilic part includes a polysiloxane having a hydrophilic group, The hydrophilic group is at least one selected from the group consisting of amino group, hydroxyl group, ether group, amide group, carboxyl group and its anhydride group, sulfonic acid group, sulfinic acid, phosphate group, phosphite group, and phosphine phosphate group,

b) Add an aqueous medium to the mixture obtained in step a) under dynamic action and emulsify it to form an emulsified composition, wherein in the emulsified composition, the monomer composition serves as a continuous phase, and the aqueous medium as a dispersed phase;

c) subjecting the emulsified composition to polymerization reaction.

Effect of the invention

Through the implementation of the above technical solutions, the present invention can obtain the following technical effects:

(1) The manufacturing method of porous materials of the present invention is based on the high internal phase emulsion template method and uses Janus particles with good structure and performance partitioning as solid emulsifiers. The Janus particles have a hydrophilic part and a hydrophobic part, and the hydrophilic part includes polysiloxane with specific hydrophilic groups.

Through the design of the hydrophilic group of the present invention, the hydrophilic-lipophilic balance can be adjusted more easily and at a lower cost, so the anchor can be stabilized even for different types of monomer compositions (oil phases). Located at the water-oil interface, it has large interfacial desorption energy, can effectively stabilize water-in-oil high internal phase emulsions, and can provide fine control of pore structure. Therefore, the manufacturing method of the present invention can easily adjust the pore structure and properties of the resulting porous material at low cost, and is environmentally friendly.

At the same time, since Janus particles can be firmly anchored to the interface after continuous phase polymerization, through the design of the hydrophilic group of the present invention, functional groups can be introduced to facilitate the function of the Janus particles anchoring the porous material at the interface. Chemical expansion, the resulting porous material can have abundant and stable functional expansion sites, making it a basic platform for more applications.

Moreover, the present invention has a simple manufacturing system and convenient post-processing, which can avoid the use of a large amount of small molecule surfactants (even the use of small molecule surfactants) and subsequent washing, thereby achieving environmental friendliness and cost savings.

(2) By adjusting the above-mentioned specific Janus particle dosage, continuous phase cross-linking degree, internal phase volume fraction, etc., the present invention can obtain porous materials with adjustable pore structure and adjustable performance, and can provide abundant and stable functional expansion sites. .

(3) By using the above-mentioned specific Janus particles with good structure and performance partitioning as solid emulsifiers in the high internal phase emulsion template method, the obtained can be effectively adjusted even for different kinds of monomer compositions (oil phases). The pore structure of porous materials.

Description of the drawings

Figure 1 is a schematic diagram showing the process of obtaining porous materials through the high internal phase emulsion method of the present invention and the pore structure of the porous materials, in which a) schematically shows the composition of the emulsified composition, and b) schematically shows the obtained porous material. Material composition, c) shows a scanning electron microscope photograph of the porous material obtained in Example 1 of the present invention.

FIG. 2 is a scanning electron microscope photograph illustrating Janus particles used in the Examples.

FIG. 3 shows the porous material obtained in Example 1 of the present invention and its scanning electron micrograph.

Detailed ways

The content of the present invention will be described in detail below. The technical features described below will be described based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted:

In this specification, the term "Janus particles" refers to Janus particles in a broad sense in this field, that is, they can not only be particles with asymmetrical structure and morphology (anisotropy), but also particles with asymmetrical composition and properties, or A little bit of both.

In this specification, the term “(meth)acrylate” includes “methacrylate” and “acrylate”; the term “(meth)acrylic acid” includes “methacrylic acid” and “acrylic acid”. The meaning of "(meth)acrylamide" used includes the meanings of "methacrylamide" and "acrylamide".

In this specification, the numerical range represented by "numeric value A to numerical value B" refers to the range including the endpoint values A and B.

In this specification, the numerical range expressed using "above" or "below" refers to the numerical range including the current number.

In this specification, the meaning of "can" includes both the meaning of performing certain processing and the meaning of not performing certain processing.

In this specification, the use of "optional" or "optional" indicates the use or non-use of certain substances, components, execution steps, applied conditions and other factors.

In this specification, the unit names used are all international standard unit names, and unless otherwise stated, the "%" used indicates weight or mass percentage.

In this specification, unless otherwise stated, the "particle size" used refers to the "average particle size", which can be measured by a commercial particle size analyzer or an electron scanning microscope.

In this specification, the "pore" used refers to the general term for all pore structures in porous materials, and includes "cavities" and "pore windows".

In this specification, the "pores" used refer to the pores in porous materials obtained by removing the internal phase droplets in the emulsion template.

In this specification, the "pore window" used refers to a circular window that realizes the hole diameter in the open cell structure of the porous material.

In this specification, references to "some specific/preferred embodiments", "other specific/preferred embodiments", "implementations", etc. refer to the specific elements described related to the embodiment (for example, Features, structures, properties and/or characteristics) are included in at least one embodiment described herein and may or may not be present in other embodiments. Additionally, it is to be understood that the described elements may be combined in various embodiments in any suitable manner.

<<Manufacturing method of porous materials>>

The manufacturing method of the porous material of the present invention includes: a) mixing a monomer composition containing a lipophilic monomer and Janus particles, wherein the surface of the Janus particles is equipped with a hydrophilic part and a hydrophobic part, and the hydrophilic part contains a hydrophilic part. Polysiloxane with water-based group, the hydrophilic group is selected from amino group, hydroxyl group, ether group, amide group, carboxyl group and its anhydride group, sulfonic acid group, sulfinic acid, phosphoric acid group, phosphite group , at least one of phosphine phosphate groups; b) add an aqueous medium to the mixture obtained in step a) under dynamic action and emulsify to form an emulsified composition, wherein in the emulsified composition, the monomer The composition serves as a continuous phase, and the aqueous medium serves as a dispersed phase; c) polymerizing the emulsified composition.

The manufacturing method of the porous material of the present invention is based on the high internal phase emulsion polymerization method. By adopting the manufacturing method of the porous material of the present invention, a porous material with adjustable pore structure and adjustable performance, which can provide abundant and stable functional expansion sites, is easy to operate and has excellent environmental friendliness at low cost.

In the present invention, the term "pore structure is adjustable" means that the pores of the obtained porous material can have only a closed cell structure (sometimes also called an independent cell structure) or only an open cell structure (sometimes also called an independent cell structure). through-cell structure), or has a semi-open and semi-closed cell structure (a cell structure in which a closed cell structure and an open cell structure are mixed), and the hole diameter (when present, the opening degree and the hole window diameter, etc.) Can be adjusted at will.

In some preferred embodiments, the pore diameter of the resulting porous structure can reach ≥1 μm, preferably ≥5 μm, more preferably 10-2000 μm, and more preferably 20-1500 μm.

Additionally, in some preferred embodiments, the porous material has an open cell structure. In some more preferred embodiments, the openness of the open cell structure of the porous material is preferably from 0.1 to 30%, more preferably from 0.2 to 10%. In other more preferred embodiments, the diameter of the pore windows in the open cell structure of the porous material is preferably 1 to 500 μm, more preferably 5 to 200 μm.

The hole diameter, pore window diameter, and opening degree of the porous structure are calculated as in the examples described below.

Each of the above steps will be described in detail below.

<Step a)>

In this step, a monomer composition including a lipophilic monomer and Janus particles are mixed, wherein the surface of the Janus particles is equipped with a hydrophilic part and a hydrophobic part, and the hydrophilic part includes polysilica having a hydrophilic group. Oxane, the hydrophilic group is at least one selected from the group consisting of amino group, hydroxyl group, ether group, amide group, carboxyl group and its anhydride group, sulfonic acid group, sulfinic acid, phosphate group, phosphite group, and phosphine phosphate group. A sort of.

In some preferred embodiments, relative to the total mass of the monomer composition, the amount of Janus particles is preferably 0.01 to 50 mass%, more preferably 1 to 30 mass%, and more preferably 2 to 20 mass% %.

In this step, there is no particular restriction on the mixing method of the monomer composition and Janus particles. Stirring, shaking, vortexing, ultrasonic waves, etc. can be applied during the mixing process as needed.

(monomer composition)

The monomer compositions of the present invention are used to form the continuous phase in high internal phase emulsion processes and to form the polymer matrix of porous materials.

Since the present invention uses Janus particles as the solid emulsifier in high internal phase emulsion polymerization, as long as the monomer composition containing the lipophilic monomer can form a continuous phase as an oil phase in the aqueous medium and perform emulsion polymerization, then for the monomer composition The specific composition of the body composition is not particularly limited.

In some specific embodiments, the monomer composition of the present invention may comprise only monomers having one polymerizable group, that is, the polymer matrix of the porous material formed from the monomer composition of the present invention is linear. In other specific embodiments, the monomer composition of the present invention may include monomers with two or more polymerizable groups (sometimes also referred to as cross-linking monomers), that is, the monomer composition of the present invention The polymer matrix of the resulting porous material is cross-linked.

In some preferred embodiments, from the perspective of obtaining the porous material of the present invention more easily, the lipophilic monomer contained in the monomer composition of the present invention is selected from the group consisting of styrenic monomers, (methyl) At least one kind selected from the group consisting of acrylate monomers, olefin monomers, vinyl ether monomers, vinyl ester monomers, and acetal monomers. In some more preferred embodiments, from the viewpoint of further obtaining the porous material of the present invention more easily, the lipophilic monomer is at least one selected from the group consisting of styrenic monomers and (meth)acrylate monomers. kind.

Examples of styrenic monomers include, but are not limited to, styrenic monomers having one vinyl group, such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene Styrene, ethylstyrene, etc.; styrenic monomers with two or more vinyl groups, such as divinylbenzene, m-trivinylbenzene, etc. These monomers can be used alone or in combination of two or more.

Examples of (meth)acrylate monomers include, but are not limited to, (meth)acrylate monomers having one (meth)acrylate group, for example, alkyl (meth)acrylate (preferably having Alkyl groups with C1 to 18, more preferably alkyl groups with C1 to 12, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso(meth)acrylate Propyl ester, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, etc.), (meth)acrylate base) hydroxyalkyl acrylate (preferably having a hydroxyalkyl group of C1 to 18, more preferably having a hydroxyalkyl group of C1 to 12, such as hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, (Hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, tert-butyl (meth)acrylate, etc.), (meth)acrylates with epoxy groups (such as glycidyl (meth)acrylate ); (meth)acrylate monomers with two or more (meth)acrylate groups, for example, di(meth)acrylate monomers (such as ethylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, etc.), tri(meth)acrylate monomers (such as glyceryl tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc.) Methacrylate), etc., tetra(meth)acrylate monomers (such as pentaerythritol tetra(meth)acrylate), penta(meth)acrylate monomers (such as dipentaerythritol penta(meth)acrylate) ester), hexa(meth)acrylate monomers (such as dipentaerythritol hexa(meth)acrylate), etc. These monomers can be used alone or in combination of two or more.

Within the scope that does not impair the effects of the present invention, the monomer composition of the present invention may include hydrophilic monomers. Examples of hydrophilic monomers include but are not limited to (meth)acrylic acid, (meth)acrylamide, Vinyl alcohol-based monomers, pyrrolidone-based monomers, etc.

In some preferred embodiments, in the monomer composition, relative to the total mass of all monomers, the content of the lipophilic monomer is preferably 50 mass% or more, more preferably 60 mass% or more, and still more preferably It is 70 mass % or more, more preferably 80 mass % or more, still more preferably 90 mass % or more. In other preferred embodiments, in the monomer composition, relative to the total mass of all monomers, the content of the hydrophilic monomer is preferably 50 mass% or less, more preferably 40 mass% or less, and still more It is preferably 30 mass% or less, still more preferably 20 mass% or less, still more preferably 10 mass% or less.

In addition, the monomer composition of the present invention may optionally contain various additives as needed, such as initiators, chain transfer agents, oil-soluble solvents (which can be used to promote mutual dissolution between monomers), etc.

In some preferred embodiments, the monomer composition of the present invention includes an initiator from the viewpoint of conducting the polymerization reaction more easily. There is no particular restriction on the specific type of initiator, but the initiator can be selected from the group consisting of dibenzoyl peroxide, dodecanoyl peroxide, tert-butyl peroxide tert-valerate, diisopropyl peroxydicarbonate, peroxy At least one of dicumylbenzene, azobisisobutyronitrile, and azobisisoheptanitrile.

In some preferred embodiments, the content of the initiator is preferably 0.5 to 5% by mass relative to the total mass of all monomers contained in the monomer composition.

(Janus granules)

The surface of the Janus particles of the present invention has a hydrophilic part and a hydrophobic part, that is, a part of the particle surface is hydrophilic and the hydrophilicity is shown by at least the hydrophilic group of the polysiloxane contained in the hydrophilic part, The other part is hydrophobic.

Here, the hydrophilic part includes polysiloxane having a hydrophilic group, and the hydrophilic group is selected from the group consisting of amino group, hydroxyl group (silicone hydroxyl group, alcoholic hydroxyl group, phenolic hydroxyl group, etc.), ether group, amide group, carboxyl group, and It contains at least one of acid anhydride group, sulfonic acid group, sulfinic acid group, phosphate group, phosphite group and phosphine phosphate group.

As long as its surface is equipped with a hydrophilic part and a hydrophobic part and the hydrophilic part contains a polysiloxane with the above-mentioned hydrophilic group, there is no particular restriction on the specific chemical composition of the Janus particles of the present invention. It can be based on the composition of the monomer composition. and the ratio of the two phases in emulsion polymerization and other factors.

The source of the hydrophilic group of the polysiloxane in the hydrophilic part of the Janus particles of the present invention is not particularly limited. It can be the hydrophilic group of the polysiloxane itself, or it can be the hydrophilic group of the polysiloxane. A hydrophilic group obtained by modifying alkane.

In addition, in some cases, from the viewpoint of further saving costs and further improving environmental friendliness, the hydrophilic group of the polysiloxane contained in the hydrophilic part of the Janus particles of the present invention may even preferably be only hydroxyl groups. (e.g. silanol).

In addition, in addition to the above-mentioned polysiloxanes, the hydrophilic portion of the Janus particles of the present invention may also contain other polymers, inorganic substances, or both. Examples of monomers that constitute the other polymers include, but are not limited to, acrylic monomers, pyrrolidone monomers, acrylamide monomers, (poly)ethylene glycol monomers, (poly)propylene glycol monomers, silicone Alkane monomers, etc. These monomers can be used alone or in combination of two or more. Examples of inorganic substances include, but are not limited to, silica, titanium dioxide, alumina, and the like. These inorganic substances can be used individually or in combination of two or more.

In some preferred embodiments, the hydrophilic portion of the Janus particles of the present invention preferably contains only polysiloxanes having the hydrophilic groups described above.

The hydrophobic portion of the Janus particles of the present invention preferably includes a hydrophobic polymer. In the present invention, the specific composition of the hydrophobic polymer constituting the hydrophobic part is not particularly limited. The hydrophobic polymer can be any resin (thermoplastic or thermosetting) or elastomer (thermoplastic or thermosetting). Here, resin refers to a polymer compound that does not exhibit rubber-like elasticity at room temperature; elastomer refers to a polymer compound that exhibits rubber-like elasticity at room temperature.

In some specific embodiments, in this case, examples of monomers forming the resin of the hydrophobic polymer include, but are not limited to, styrenic monomers (monofunctional and difunctional or above), (meth)acrylates Monomers (monofunctional and difunctional or more), vinyl ester monomers (monofunctional or more than difunctional), silane monomers, siloxane monomers, olefin monomers, acetal monomers, etc. . These monomers can be used alone or in combination of two or more. In some more preferred embodiments, the resin as the hydrophobic polymer is preferably at least one selected from the group consisting of styrenic resins and (meth)acrylate resins.

In other specific embodiments, examples of elastomers that are hydrophobic polymers include, but are not limited to, polyamide-based polymers, polyurethane-based polymers, polyester-based polymers, polyisoprene rubber (natural sources or synthetic sources), chloroprene rubber, butyl rubber, butadiene rubber, nitrile rubber, silicone rubber, styrenic copolymers (for example, styrene/conjugated diene copolymers, for example, styrene/butadiene ethylene copolymer, styrene/butadiene/styrene copolymer, styrene/isoprene copolymer, styrene/isoprene/styrene copolymer, styrene/butadiene/isoprene copolymer Copolymer, styrene/butadiene/isoprene/styrene copolymer, styrene/butadiene/ethylene/styrene copolymer, styrene/butadiene/propylene/styrene copolymer, etc.; styrene Ethylene/olefin copolymers, such as styrene/hexene/butylene/styrene copolymer, styrene/ethylene/propylene/styrene copolymer, styrene/ethylene/butylene/styrene copolymer, etc.; etc. ), (meth)acrylate polymer. These monomers can be used alone or in combination of two or more. In some more preferred embodiments, the elastomer as the hydrophobic polymer is more preferably selected from the group consisting of polyisoprene rubber, chloroprene rubber, butyl rubber, butadiene rubber, nitrile rubber, styrenic polymers At least one of polymers and (meth)acrylate polymers.

In other preferred embodiments, the hydrophobic portions of the Janus particles of the present invention are preferably cross-linked.

In some particularly preferred embodiments, the entire particle of the Janus particles of the present invention is divided into the above-mentioned hydrophilic part and the above-mentioned hydrophobic part.

In addition, the hydrophobic part of the Janus particles of the present invention can be hollow, porous, or solid as needed.

In the present invention, there is no particular restriction on the structural morphology of the Janus particles of the present invention. For example, the Janus particles of the present invention can be spherical, rod-shaped, butterfly-shaped, mushroom-shaped, bullet-shaped, cone-shaped, cylindrical, dish-shaped, or hamburger-shaped. , dumbbell-like, chain-like, semi-raspberry-like, raspberry-like, or snowman-like shapes, and can be appropriately selected according to factors such as the composition of the monomer composition and the ratio of the two phases in the emulsion polymerization. From the perspective of better realizing the technical effects of the present invention, the Janus particles of the present invention are preferably particles with an asymmetric (anisotropic) structure and morphology, and are more preferably particles with a snowman shape. In the present invention, the term "snowman shape" refers to a three-dimensional structure formed by stacking two spheres (or approximate spheres) of the same or different sizes in a partially overlapping manner. In the case where the Janus particles of the present invention are snowman-shaped particles, the ratio of the diameters of the two spheres constituting the "snowman shape" is preferably 1:4 to 4:1, so that the Janus particles tend to adjust the size of the hydrophilic end, that is, The hydrophilic and lipophilic balance of the particles can be adjusted more conveniently. Furthermore, in some particularly preferred embodiments, the two spheres (or approximate spheres) constituting the snowman-like structure of the Janus particles of the present invention are respectively the above-mentioned hydrophilic part and the above-mentioned hydrophobic part.

The size of the Janus particles of the present invention is not particularly limited as long as it can function as a solid emulsifier, and can be appropriately adjusted according to factors such as the composition of the monomer composition and the ratio of the two phases in emulsion polymerization. In some specific embodiments, from the perspective of better realizing the technical effects of the present invention, the size of the Janus particles of the present invention is preferably 250~1000nm, more preferably 400~800nm, and even more preferably 500nm. ~700nm. The size of the Janus particles of the present invention can be measured by means well known in the art, such as by scanning electron microscopy (SEM).

In the present invention, Janus particles can be prepared by methods commonly used in the art, for example, by emulsion polymerization, seed emulsion polymerization, dispersion polymerization, dispersion polymerization-seed emulsion polymerization, phase separation, micro-processing and Self-assembly etc. to prepare.

In some particularly preferred embodiments, when the Janus particles of the present invention are in the shape of a snowman, the Janus particles of the present invention are obtained by the following method:

(1) Preparation of a seed emulsion containing particles of a homemade or commercially obtained hydrophobic polymer (later formed into the hydrophobic moiety),

(2) Will contain such as 3-(methacryloyloxy)propyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, 3-(methacryloyloxy)propyltripropyl Oxysilane, 3-(methacryloyloxy)propyltrichlorosilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane Chlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, 3-enbutyltrimethoxysilane, 3-enbutyltriethoxysilane, 3- Emulsion compositions of silane coupling agents containing double bonds such as enbutyltrichlorosilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltrichlorosilane, etc. are added to the seed emulsion to obtain a mixture, and optionally allowed to swell for any length of time,

(3) Allow the silane coupling agent containing double bonds to undergo polymerization and hydrolysis condensation reactions to obtain composite Janus particles.

For example, more specifically, the manufacturing methods of composite Janus particles described in Patent Document 1 and Patent Document 2 can be used.

(other components)

In addition to the monomer composition and Janus particles, other components may be mixed in this step as desired. Examples of other components include, but are not limited to, surfactants, fillers, plasticizers, flame retardants, UV absorbers, colorants, heat stabilizers, etc. in addition to Janus particles. The amounts of these other components may be those known in the art.

In some preferred embodiments, no surfactants other than Janus particles are mixed.

<Step b)>

In this step, an aqueous medium is added to the mixture obtained in step a) and emulsified under dynamic action to form an emulsified composition, in which the monomer composition serves as a continuous phase and the aqueous medium serves as a dispersed phase. .

The volume ratio of the monomer composition in the emulsified composition is not particularly limited and can be appropriately adjusted according to factors such as the required pore structure of the porous material. In some preferred embodiments, from the perspective of better adjusting the pore structure of the resulting porous material and better ensuring the desired structure and mechanical properties of the resulting porous material, the proportion of the monomer composition in the emulsified composition It is preferably 10 to 95% based on volume conversion. In some more specific embodiments, for the preparation of porous materials containing only closed cell structures, the proportion of the monomer composition in the emulsified composition is preferably 10 to 70% based on volume conversion, and more preferably is 15% to less than 55%. In other more specific embodiments, for the preparation of porous materials containing open cell structures, in the emulsified composition, the proportion of the monomer composition is preferably 10 to 70% based on volume conversion, and more preferably is 55~90%.

The specific composition of the aqueous medium of the present invention is not particularly limited and can be appropriately adjusted according to actual needs. In the present invention, the aqueous medium includes an aqueous solvent, and the aqueous solvent may be water or a mixture of water and a water-soluble solvent. Examples of water-soluble solvents include, but are not limited to, alcohol solvents, amine solvents, ether solvents, ketone solvents, and the like.

In addition, in the present invention, the aqueous medium may optionally contain an electrolyte. In some preferred embodiments, the electrolyte is at least one selected from calcium chloride, sodium chloride, and potassium chloride.

In some more preferred embodiments, from the perspective of better obtaining the technical effects of the present invention, the aqueous medium is water or water with an electrolyte dissolved therein.

The method of adding the aqueous medium is not particularly limited as long as the emulsification can be smoothly performed and an emulsified composition with the monomer composition as the continuous phase and the aqueous medium as the dispersed phase is obtained. To the composition including the monomer composition and Janus particles, the aqueous medium may be added at once or in batches.

In some preferred embodiments, from the viewpoint of easier emulsification and easier adjustment of the pore structure of the resulting porous material, the aqueous medium is preferably added in batches.

In some more preferred embodiments, relative to the total mass of the aqueous medium to be added, the amount of the aqueous medium added each time is preferably 5 to 40%, more preferably 20 to 30%. In other more preferred embodiments, the emulsification time between two additions of the aqueous medium is preferably 10 seconds to 15 minutes, more preferably 30 seconds to 10 minutes, and even more preferably 1 minute to 5 minutes.

Additionally, in some preferred embodiments, the addition of the aqueous medium is performed without dynamic effects. In other preferred embodiments, the addition of the aqueous medium is also performed under dynamic action. Here, the dynamic action exerted when adding the aqueous medium may be the same as or different from the dynamic action exerted during emulsification described later, and is preferably the same as the dynamic action exerted during emulsification described later.

In the present invention, the dynamic action exerted during emulsification can be exerted by methods known in the art, for example, stirring, shearing, oscillation, vortexing, ultrasonic waves, etc. can be applied. In some preferred embodiments, from the perspective of easy operation and easier emulsification, the dynamic effect is preferably applied by stirring, shearing or vortexing, more preferably by high-speed stirring (the rotation speed is preferably 300 ~4000r/min, more preferably 500~3000r/min), high-speed shear (preferably 2000~23000r/min, more preferably 3000~10000r/min), or vortex.

<Step c)>

In this step, the emulsified composition of the present invention is subjected to polymerization reaction. There is no particular restriction on the mechanism of polymerization carried out in the present invention, but preferably, the polymerization of the present invention is carried out based on free radical polymerization.

The polymerization temperature in the present invention is not particularly limited and can be appropriately adjusted according to factors such as the respective compositions of the monomer composition and the aqueous medium, and the ratio between the two. In some preferred embodiments, from the perspective of being more conducive to the production of porous materials and saving production costs, the polymerization temperature is preferably 50 to 100°C, more preferably 55 to 80°C, and even more preferably 65 ~75℃.

The polymerization time of the present invention is not particularly limited and can be appropriately adjusted according to factors such as the respective compositions of the monomer composition and the aqueous medium, and the ratio between the two. In some preferred embodiments, from the perspective of ensuring the production of porous materials and improving production efficiency, the polymerization time is preferably 7 to 48 hours, and more preferably 12 to 24 hours.

In addition, the polymerization atmosphere of the present invention is not particularly limited. The polymerization can be carried out in an atmosphere of air, in an atmosphere of air with an adjusted oxygen partial pressure, or in an atmosphere of inert gas such as nitrogen and helium.

In addition, in some preferred embodiments, the emulsified composition of the present invention can be introduced into a suitable mold and then polymerized. In this case, porous materials with desired shapes can be produced more conveniently.

<Other steps>

The manufacturing method of the porous material of the present invention may further include other steps known in the art as needed, such as washing, drying, cutting and other steps of the obtained porous material.

Each of these other steps can be performed using methods known in the art.

<Specific example>

In some specific embodiments, the manufacturing method of the porous material of the present invention can be performed as follows:

Janus particles are dispersed in the monomer composition in which the initiator is dissolved to form an oil phase.

The water phase (aqueous medium) is added to the oil phase in small amounts and multiple times, and the intervals between each two additions are supplemented by a certain period of emulsification operation to obtain a highly viscous internal phase emulsified composition.

The prepared high internal phase emulsified composition is transferred to a mold, sealed, and placed in a high temperature environment for polymerization.

After the resulting material is removed from the mold, it is vacuum dried to obtain the final porous material.

<<Porous materials>>

The porous material of the present invention includes a polymer substrate and pores distributed therein. The inner wall of the pores includes Janus particles. The surface of the Janus particles is equipped with a hydrophilic part and a hydrophobic part. The hydrophilic part contains hydrophilic groups. Polysiloxane, the hydrophilic group is selected from amino group, hydroxyl group, ether group, amide group, carboxyl group and its anhydride group, sulfonic acid group, sulfinic acid, phosphate group, phosphite group, phosphine phosphate group at least one of them. In addition, the pore diameter of the porous structure in the porous material of the present invention is ≥1 μm, preferably ≥5 μm, more preferably 10 to 2000 μm, and even more preferably 20 to 1500 μm.

The porous material of the present invention has adjustable pore structure and adjustable performance, and can provide abundant and stable functional expansion sites.

In the present invention, the pores of the porous material may have only a closed cell structure (sometimes also called an independent cell structure), only have an open cell structure (sometimes also called a through-cell structure), or have semi-open and semi-closed cells. Cell structure (cell structure in which closed cell structure and open cell structure are mixed).

In some preferred embodiments, the porous material has an open cell structure. In some more preferred embodiments, the openness of the open cell structure of the porous material is preferably from 0.1 to 30%, more preferably from 0.2 to 10%. In other more preferred embodiments, the diameter of the pore windows in the open cell structure of the porous material is preferably 1 to 500 μm, more preferably 5 to 200 μm.

In addition, in some preferred embodiments, relative to the total mass of the polymer matrix of the porous material, the content of Janus particles is preferably 0.01 to 50 mass%, more preferably 1 to 30 mass%, and even more preferably 2 to 20% by mass.

The details of the monomer composition forming the polymer matrix of the porous material and the Janus particles are the same as described in the above <<Production method of porous material>>, and will not be described again here.

In addition, there is no particular limitation on the method for producing the porous material of the present invention. As long as the above-mentioned structure of the porous material of the present invention can be obtained, it can be obtained by various methods known in the art. However, in some particularly preferred embodiments, from the viewpoint of making it easier to obtain the porous material of the present invention, the porous material of the present invention can be obtained by the manufacturing method of the porous material of the present invention. The details of the manufacturing method are as described in the above <<Manufacturing Method of Porous Materials>> and will not be described again here.

<<Methods for adjusting the pore structure of porous materials>>

The method for adjusting the pore structure of the porous material of the present invention includes: a) mixing a monomer composition containing a lipophilic monomer and Janus particles, wherein the surface of the Janus particles is equipped with a hydrophilic part and a hydrophobic part, and the hydrophilic part contains Polysiloxane with hydrophilic groups, the hydrophilic groups are selected from amino groups, hydroxyl groups, ether groups, amide groups, carboxyl groups and their anhydride groups, sulfonic acid groups, sulfinic acid, phosphoric acid groups, and phosphorous acid at least one of base and phosphine phosphate group; b) add an aqueous medium to the mixture obtained in step a) under dynamic action and emulsify to form an emulsified composition, wherein in the emulsified composition, the monomer composition is as The continuous phase and the aqueous medium serve as the dispersed phase; c) polymerize the emulsified composition.

By using Janus particles with good structure and performance partitioning as solid emulsifiers in the high internal phase emulsion template method as described above, even for monomer compositions of arbitrary compositions, it can be easily produced in the high internal phase emulsion method at low prices. Cost modulates the pore structure of porous materials.

Each step that may be included in the method for adjusting the pore structure of the porous material of the present invention has been described in the above <<Production method of porous material>> and will not be described again here.

<<Example>>

The present invention will be described in more detail below using examples, but these examples do not limit the scope of the present invention.

<Determination of pore structure>

In the present invention, the porous materials prepared in each example were observed through a scanning electron microscope (SEM) model JSM-7900F manufactured by JEOL (Japan). Specifically, at least 200 pore structures in each porous material were observed.

The hole diameter of the porous structure is calculated based on the following equation (1).

Among them, D _p is the Sauter average diameter of the holes within the specified field of view, and d _pi is the hole diameter directly measured within the field of view.

The pore window diameter of the porous structure is calculated based on the following equation (2).

Among them, D _w is the area-weighted average diameter of the hole and window within the same field of view when statistics are made as D _p , and d _wi is the diameter of the hole and window directly measured within the field of view.

Calculate the openness of the porous structure based on the following equation (3)

Among them, R _wp is the ratio of twice the number of holes counted to the number of holes counted within the field of view when D _p and D _w are counted, and can be calculated as Equation (4).

<Example 1>

Disperse 0.1g Janus particles (snowman shape, the hydrophilic end is polysiloxane with only silanol as a hydrophilic group, the hydrophobic end is cross-linked polystyrene hollow particles, size is 700nm) in 1.25mL monomer composition to form an oil phase; the monomer composition also contains initiator azobisisobutyronitrile in an amount of 1% by mass relative to all monomers. Among them, the main monomer is butyl acrylate, and the cross-linking agent is ethylene glycol dimethacrylate (the volume ratio of the main monomer to the cross-linking agent is 30/1). Relative to the monomer composition, the amount of Janus particles is 10wt%.

Add 3.75 mL of ultrapure water to the oil phase in 5 times, with each addition amount being 0.75 mL, and vortex for 1 min between additions. After all the water is added, continue vortexing for 3 minutes to obtain a uniform emulsified composition. In the emulsified composition, the proportion of the monomer composition is 25% based on volume conversion.

The obtained emulsion was moved to a glass mold and sealed. After constant temperature treatment at 70°C for 24 hours, the polymerized and solidified material was taken out and dried in a vacuum oven at 70°C for 4 hours.

Scanning electron microscopy characterization showed that the obtained porous material included an open cell structure with a pore diameter of 136 μm, a pore window diameter of 15.7 μm at the connection point between the pores, and an opening degree of 1.57%.

<Example 2>

Disperse 0.2g Janus particles (snowman shape, the hydrophilic end is polysiloxane with only silanol as a hydrophilic group, the hydrophobic end is cross-linked polystyrene hollow particles, size is 700nm) in 1.25mL monomer composition to form an oil phase; the monomer composition also contains initiator azobisisobutyronitrile in an amount of 1% by mass relative to all monomers. Among them, the main monomer is butyl acrylate, and the cross-linking agent is ethylene glycol dimethacrylate (the volume ratio of the main monomer to the cross-linking agent is 30/1). Relative to the monomer composition, the amount of Janus particles is 20wt%.

Add 3.75 mL of ultrapure water to the oil phase in 5 times, with the amount added each time being approximately 0.75 mL, and vortexing for 1 min between additions. After all the water is added, continue vortexing for 3 minutes to obtain a uniform emulsified composition. In the emulsified composition, the proportion of the monomer composition is 25% based on volume conversion.

The obtained emulsion was moved to a glass mold and sealed. After constant temperature treatment at 70°C for 24 hours, the polymerized and solidified material was taken out and dried in a vacuum oven at 70°C for 4 hours.

Scanning electron microscopy characterization showed that the obtained porous material included an open cell structure with a pore diameter of 78 μm, a pore window diameter of 10.4 μm at the connection point between the pores, and an opening degree of 0.89%.

<Example 3>

Disperse 0.05g Janus particles (snowman-shaped, the hydrophilic end is polysiloxane with only silanol as a hydrophilic group, the hydrophobic end is cross-linked polystyrene hollow particles, size is 700nm) in 1.25mL monomer composition to form an oil phase; the monomer composition also contains initiator azobisisobutyronitrile in an amount of 1% by mass relative to all monomers. The main monomer is butyl acrylate, and the cross-linking agent is ethylene glycol dimethacrylate (the volume ratio of main monomer to cross-linking agent is 30/1). Relative to the monomer composition, the dosage of Janus particles is 5wt%.

Add 3.75 mL of ultrapure water to the oil phase in 5 times, with the amount added each time being 0.75 mL, and vortexing for 1 min between additions. After all the water is added, continue vortexing for 3 minutes to obtain a uniform emulsified composition. In the emulsified composition, the proportion of the monomer composition is 25% based on volume conversion.

The obtained emulsion was moved to a glass mold and sealed. After constant temperature treatment at 70°C for 24 hours, the polymerized and solidified material was taken out and dried in a vacuum oven at 70°C for 4 hours.

Scanning electron microscopy characterization showed that the obtained porous material included an open cell structure with a pore diameter of 207 μm, a pore window diameter of 33.6 μm at the connection point between the pores, and an opening degree of 3.50%.

<Example 4>

Disperse 0.1g of Janus particles (snowman-shaped, the hydrophilic end is polysiloxane with only silanol as a hydrophilic group, the hydrophobic end is cross-linked polystyrene hollow particles, size is 700nm) in 1 mL monomer combination in the composition to form an oil phase; the monomer composition also contains 1 mass% of the initiator azobisisobutyronitrile relative to all monomers. The main monomer is butyl acrylate, and the cross-linking agent is ethylene glycol dimethacrylate (the volume ratio of main monomer to cross-linking agent is 30/1). Relative to the monomer composition, the dosage of Janus particles is 10wt%.

Add 4 mL of ultrapure water to the oil phase in 8 times, with the amount added each time being about 0.5 mL, and vortexing for 1 min between additions. After all the water is added, continue vortexing for 3 minutes to obtain a uniform emulsified composition. In the emulsified composition, the proportion of the monomer composition is 20% based on volume conversion.

The obtained emulsion was moved to a glass mold and sealed. After constant temperature treatment at 70°C for 24 hours, the polymerized and solidified material was taken out and dried in a vacuum oven at 70°C for 4 hours.

Scanning electron microscopy characterization showed that the obtained porous material included an open cell structure with a pore diameter of 211 μm, a pore window diameter of 29.3 μm at the connection point between the pores, and an opening degree of 2.78%.

<Example 5>

Disperse 0.1g Janus particles (snowman shape, the hydrophilic end is polysiloxane with only silanol as a hydrophilic group, the hydrophobic end is cross-linked polystyrene hollow particles, size is 700nm) in 1.25mL monomer composition to form an oil phase; the monomer composition also contains initiator azobisisobutyronitrile in an amount of 1% by mass relative to all monomers. The main monomer is butyl acrylate, and the cross-linking agent is ethylene glycol dimethacrylate (the volume ratio of the main monomer to the cross-linking agent is 3/1). Relative to the monomer composition, the dosage of Janus particles is 10wt%%.

Add 3.75 mL of ultrapure water to the oil phase in fractions, with the amount added each time being about 0.5 mL, and vortex for 1 min between additions. After all the water is added, continue vortexing for 3 minutes to obtain a uniform emulsified composition. In the emulsified composition, the proportion of the monomer composition is 25% based on volume conversion.

The obtained emulsion was moved to a glass mold and sealed. After constant temperature treatment at 70°C for 24 hours, the polymerized and solidified material was taken out and dried in a vacuum oven at 70°C for 4 hours.

Scanning electron microscopy characterization showed that the obtained porous material included an open cell structure with a pore diameter of 100 μm, a pore window diameter of 8.7 μm at the connection point between the pores, and an opening degree of 0.28%.

Claims (13)

1. A method of manufacturing porous materials, characterized by comprising: a) mixing a monomer composition including a lipophilic monomer and Janus particles, wherein the surface of the Janus particles is provided with a hydrophilic part and a hydrophobic part, and the hydrophilic part includes a polysiloxane having a hydrophilic group, The hydrophilic group is at least one selected from the group consisting of amino group, hydroxyl group, ether group, amide group, carboxyl group and its anhydride group, sulfonic acid group, sulfinic acid, phosphate group, phosphite group, and phosphine phosphate group; b) Add an aqueous medium to the mixture obtained in step a) and emulsify it under dynamic action to form an emulsified composition, wherein in the emulsified composition, the monomer composition serves as a continuous phase, and the aqueous medium as a dispersed phase; c) subjecting the emulsified composition to polymerization reaction. 2. The manufacturing method according to claim 1, characterized in that in step a), the lipophilic monomer is at least one selected from the group consisting of styrene-based monomers and (meth)acrylate-based monomers. . 3. The manufacturing method according to claim 1 or 2, characterized in that, in step a), the Janus particles are in the shape of a snowman, and the size of the Janus particles is 250-1000 nm; in the Janus particles, the The hydrophobic portion contains hydrophobic polymers. 4. The manufacturing method according to any one of claims 1 to 3, characterized in that in step a), the amount of Janus particles is 0.01 to 50 mass relative to the total mass of the monomer composition. %; In step a), no surfactant other than the Janus particles may be used. 5. The manufacturing method according to any one of claims 1 to 4, characterized in that in step b), in the emulsified composition, the proportion of the monomer composition is 10 to 95% based on volume conversion. . 6. The manufacturing method according to any one of claims 1 to 5, wherein in step b), the aqueous medium is added in batches. 7. The manufacturing method according to claim 6, wherein in step b), the emulsification time between two additions is 10 seconds to 15 minutes. 8. The manufacturing method according to any one of claims 1 to 7, characterized in that in step c), the polymerization temperature is 50-100°C and the polymerization time is 7-48 hours. 9. A porous material, characterized in that it includes a polymer substrate and pores distributed therein, and Janus particles are included at the inner wall of the pores, and the surface of the Janus particles is provided with a hydrophilic part and a hydrophobic part, and the hydrophilic part is Part of it contains polysiloxane with hydrophilic groups, the hydrophilic groups are selected from amino groups, hydroxyl groups, ether groups, amide groups, carboxyl groups and their anhydride groups, sulfonic acid groups, sulfinic acid, phosphate groups , at least one of phosphite group and phosphine phosphate group, and the hole diameter is 1 μm or more. 10. The porous material according to claim 9, wherein the monomer forming the polymer base material is at least one selected from the group consisting of styrenic monomers and (meth)acrylate monomers. 11. The porous material according to claim 9 or 10, characterized in that the Janus particles are in the shape of a snowman, and the size of the Janus particles is 250 to 1000 nm. 12. The porous material according to any one of claims 9 to 11, characterized in that the porous material has an open cell structure, the porosity in the open cell structure is 0.1 to 30%, and the hole window The diameter is 1~500μm. 13. A method for adjusting the pore structure of porous materials, characterized in that it includes: a) mixing a monomer composition including a lipophilic monomer and Janus particles, wherein the surface of the Janus particles is provided with a hydrophilic part and a hydrophobic part, and the hydrophilic part includes a polysiloxane having a hydrophilic group, The hydrophilic group is at least one selected from the group consisting of amino group, hydroxyl group, ether group, amide group, carboxyl group and its anhydride group, sulfonic acid group, sulfinic acid, phosphate group, phosphite group, and phosphine phosphate group, b) Add an aqueous medium to the mixture obtained in step a) under dynamic action and emulsify it to form an emulsified composition, wherein in the emulsified composition, the monomer composition serves as a continuous phase, and the aqueous medium as a dispersed phase; c) subjecting the emulsified composition to polymerization reaction.