KR20140006317A - Mesoporous crosslinked copolymers having reactive fucntional groups - Google Patents

Abstract

The present invention provides a mesoporous crosslinked copolymer which contains the following: more than one kind of initial material including a reactive functional group which does not participate in radical reaction, and a functional group capable of radical polymerization; and a recurring unit derived from an acrylamide based crosslinking agent including one of a C3-12 hetero aromatic ring residue including a C6-20 aromatic ring and a nitrogen atom and a C3-12 hetero alicyclic ring residue including a nitrogen atom, and more than two acryloyl groups or acrylamide.

Description

Mesoporous crosslinked copolymer having reactive functional groups {MESOPOROUS CROSSLINKED COPOLYMERS HAVING REACTIVE FUCNTIONAL GROUPS}

A mesoporous crosslinkable organic material having a reactive functional group, a method for producing the same, and an application thereof.

Nanoporous materials have high void volume and specific surface area and are widely used in various applications related to adsorption, separation, sensors, and catalysts. Nanoporous materials can be distinguished according to their pore size, solid morphology, and the like, which classify them into three classes: microporous, mesoporous, and macroporous. have. Inorganic materials, zeolites and organic-inorganic composites, metal organic structures (MOFs) are typical examples of microcrystalline porous materials with high crystallinity, and include silica / aluminum silicate-based porous materials (e.g., silica aerogels, M41-S solids, etc.). ) Is a typical example of a material with mesopores. Mesoporous materials, which consist mainly of pores in the range of 2 to 50 nm, exhibit high surface area and fast diffusible mass transfer and therefore can be used in membrane materials, chromatography, catalyst carriers, gas storage through physical adsorption, and sensors. Great potential. In applying such a mesoporous material as a catalyst, a reactive membrane, a gas carrier, and an adsorbent, it may be desirable to introduce a separate reactive functional group into the material itself.

However, most of the mesoporous materials currently used are manufactured based on inorganic or organic-inorganic hybrid components, and there is a limit to introducing various functional groups into the mesoporous materials as necessary. For example, since metal oxide-based airgels, which are known to form mesopores relatively easily, are usually prepared through hydrolysis and condensation reactions, when a reactive functional group that needs to be introduced for the application is included in the starting material itself, Participation in the manufacture of the material may interfere with the formation of pore structures. Therefore, in general, when the introduction of reactive functional groups into the mesoporous material is required, the functional groups are introduced through post-synthetic modification, which increases the complexity of the manufacturing process and the time required for the production. It also increases.

In addition, the inorganic mesoporous material or the organic-inorganic hybrid mesoporous material is inherently poor in hydrothermal stability, and thus it is difficult to avoid deterioration of the material when exposed to water for a long time. The use of the reaction catalyst in an aqueous medium or the like has been a problem.

One embodiment of the present invention is to provide a mesoporous crosslinked copolymer having a high specific surface area including a plurality of mesopores, consisting only of an organic skeleton and containing a desired reactive functional group.

Another embodiment of the present invention is to provide a method for preparing such a mesoporous crosslinked copolymer in a simple process under mild conditions.

Another embodiment of the invention is directed to the use of such mesoporous crosslinked copolymers as heterogeneous catalysts or as adsorbent materials.

In one embodiment of the invention, the repeating unit derived from one or more starting materials represented by the following general formula (1):

Wherein R ₁ is a reactive functional group that does not participate in a radical reaction, A is a direct bond or an organic moiety as a linker, m and n are each independently an integer of 1 or more, and R ₂ Are radically polymerizable groups, provided that when m or n is 2 or more, each R ₁ or R ₂ is the same or different); And

Two or more (alkyl) of one or more of the aromatic ring residues of C6 to C20, the heteroaromatic ring residues of C3 to C12 comprising a nitrogen atom, and the hetero-alicyclic ring residues of C3 to C12 comprising a nitrogen atom A mesoporous crosslinked copolymer comprising a repeating unit derived from an acrylamide-based crosslinking agent having a) acryloyl group or (alkyl) acrylamide group is provided. The starting material and the crosslinking agent may be in the form of a monomer, oligomer, or polymer.

In Formula 1, R ₁ represents a hydroxy group, an alkoxy group, an isocyanate group, an amine group, a sulfonic acid group, a carboxyl group, a pyridine group, an epoxy group, or a silane-based functional group such as trimethoxysilane, phosphoric acid group, urea group, sulfonyl urea group, and aziri. It may be selected from the group consisting of dine groups, R ₂ may be a (alkyl) acrylate group such as (meth) acrylate group, (alkyl) acrylamide group such as (meth) acrylamide group, or vinyl group, A Is a direct bond or substituted or unsubstituted, such as a straight or branched alkylene group of C1 to C30, an amine group including an substituted or unsubstituted C1 to C30 alkylene residue, an ether group, a carbonyl group, an ester group, a phenylene methylene group, etc. An organic moiety comprising at least one of a substituted C 6 to C 20 aromatic ring residue and a substituted or unsubstituted C 3 to C 20 alicyclic ring residue such as a cyclohexylene group There.

The crosslinking agent is phenylenedi (alkyl) acrylamide, such as 1,3-phenylenedi (alkyl) acrylamide, 1,4-phenylenedi (alkyl) acrylamide represented by formula (2), 1,3 represented by formula (3) , 5-trialkylacryloylhexahydro-1,3,5-triazine, and acrylamide derivatives of alkylated melamine formaldehyde polymers represented by Formula 4:

(In Formula 2, each R is independently hydrogen or alkyl having 1 to 10 carbon atoms, such as a methyl group.)

(In Formula 3, each R is independently hydrogen or alkyl having 1 to 10 carbon atoms, such as a methyl group.)

Wherein each R is independently hydrogen or a straight or branched alkyl group of 1 to 10 carbon atoms, at least one R is alkyl, and R 1 is hydrogen or an alkyl group of 1 to 10 carbon atoms, such as a methyl group.

The acrylamide derivative of the alkylated melamine formaldehyde polymer may have a number average molecular weight of about 10 to about 1000.

The mesoporous crosslinked copolymer may have a form of a monolith structure including mesopores therein. The mesoporous copolymer may be in the form of a wet gel, an airgel, or a zero gel.

In another embodiment of the present invention, there is provided a process for preparing a mesoporous crosslinked copolymer having a reactive functional group, comprising the following steps:

a) at least one starting material represented by formula (1):

[Formula 1]

Wherein R ₁ , A, m, n, and R ₂ are as defined above; And

Two or more (alkyl) acryloyl groups with one of the aromatic ring residues of C6 to C20, the heteroaromatic ring residues of C3 to C12 including a nitrogen atom, and the heteroalicyclic ring residues of C3 to C12 containing a nitrogen atom, or Dissolving an acrylamide-based crosslinking agent having a (alkyl) acrylamide group in a solvent; And

b) adding a radical polymerization initiator to the reaction solution obtained in step a), dissolving and heating to form a gel.

The method for preparing the mesoporous crosslinked copolymer may include the steps of c) aging the gel obtained in step b); And d) optionally drying the gel aged in step c).

The hetero aromatic ring moiety includes a substituted or unsubstituted triazine moiety such as triaminotriazine and the like, and the hetero alicyclic ring moiety includes a substituted or unsubstituted hexahydrotriazine moiety such as hexahydrotriazine. According to another embodiment of the invention, there is provided a catalyst comprising a mesoporous crosslinked copolymer comprising a reactive functional group.

According to another embodiment of the invention, an adsorbent material is provided comprising a mesoporous crosslinked copolymer comprising a reactive functional group.

Various reactive functional groups can be included in the mesoporous organic copolymer to realize mesoporous materials having a large specific surface area and a large pore volume as well as a high functional group density (ie, a large number of functional groups per volume).

Figure 1 schematically shows an embodiment of a method for producing a mesoporous crosslinked polymer according to one embodiment of the present invention.
2 is an IR spectrum of the copolymers of Examples 1 to 3 and poly (1,3,5-triacryloylhexahydro-1,3,5-triazine) (hereinafter pTAHT).
3 is a solid carbon NMR spectrum of the copolymers of Examples 1 to 3 and pTAHT.
4 is a SEM photograph of the copolymer of Example 1. FIG.
5 is a nitrogen adsorption-desorption isotherm of the copolymers of Examples 1-3.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Thus, in some implementations, well-known techniques are not specifically described to avoid an undesirable interpretation of the present invention. Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Also, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise. Whenever a component is referred to as "including" an element throughout the specification, it is to be understood that the element may include other elements, not the exclusion of any other element, unless the context clearly dictates otherwise.

Also, singular forms include plural forms unless the context clearly dictates otherwise.

Embodiments described herein will be described with reference to schematic diagrams which are ideal illustrations of the present invention. Thus, the regions illustrated in the figures have schematic attributes and are not intended to limit the scope of the invention. Like reference numerals refer to like elements throughout.

The mesoporous crosslinked polymer provided according to one embodiment of the present invention is an aromatic ring moiety of C6 to C20, a heteroaromatic ring moiety of C3 to C12 including a nitrogen atom, and a hetero alicyclic ring of C3 to C12 including a nitrogen atom Repeating units derived from an acrylamide crosslinking agent having one of the group ring moieties and two or more (alkyl) acryloyl groups or (alkyl) acrylamide groups; And at least one start represented by Formula 1 Include repeat units derived from the substance:

[Formula 1]

Wherein R ₁ is a reactive functional group that does not participate in radical reactions, A is a direct bond or an organic moiety as a linker, m and n are each independently an integer of at least 1, and R ₂ is a radical polymerizable group, m or When n is 2 or more, each R ₁ or R ₂ is the same or different.

The hetero aromatic ring residue includes a substituted or unsubstituted triazine residue such as triaminotriazine, and the hetero alicyclic ring residue includes a substituted or unsubstituted hexahydrotriazine residue such as hexahydrotriazine.

In Formula 1, R ₁ represents a hydroxyl group, an alkoxy group, an isocyanate group, an amine group, a sulfonic acid group, a carboxyl group, a pyridine group, an epoxy group, or a silane-based functional group such as trimethoxysilane, phosphoric acid group, urea group, sulfonylurea group, and aziri. It may be selected from the group consisting of dine groups, R ₂ may be a (alkyl) acrylate group such as acrylate, methacrylate, (alkyl) acrylamide group such as acrylamide, methacrylamide, or vinyl group, A Is a direct bond or a C1 to C30 straight or branched alkylene group, a substituted or unsubstituted or an amine group having an alkylene residue of C1 to C30, an ether group, a carbonyl group, an ester group, a phenylene, a phenylene methylene group, or the like. At least one of substituted or unsubstituted C3 to C20 alicyclic ring residues such as substituted or unsubstituted C6 to C20 aromatic ring residues, and cyclohexylene groups It may be an organic residue made by . When m and n are 2 or more, each of R ₁ and R ₂ is the same or different. More specifically, the linking group A is a direct bond or a substituted or unsubstituted, straight or branched C1 to C10 alkylene group, a substituted or unsubstituted, straight or branched C1 to C10 alkylene moiety. Amine group, substituted or unsubstituted phenylene group or phenylene methylene group, substituted or unsubstituted cyclohexylene group.

Here, "substituted" or "substituted" means that at least one hydrogen present in the residue is substituted with a group selected from the group consisting of C1 to C30 alkyl groups, amino groups, hydroxy groups, and combinations thereof.

The starting material represented by Chemical Formula 1 may be in the form of a monomer, oligomer, or polymer.

In some embodiments, the starting material is one or more compounds selected from:

In formula (VII), X is SO ₃ Na, NH ₂ , or CO ₂ H, and m, n, 1 in formulas (IX) and (X) are each from 1 to 10000. The mesoporous crosslinked copolymer may include repeating units derived from different starting materials having various linkers as necessary, thereby relatively freely controlling the physical properties of the structure, such as flexibility, strength, hydrophilicity, and swelling.

In some embodiments, the crosslinker is phenylenedi (alkyl) acrylamide, such as 1,3-phenylenedi (alkyl) acrylamide, 1,4-phenylenedi (alkyl) acrylamide represented by Formula 2, Formula 3 Is selected from the group consisting of 1,3,5-tri (alkyl) acryloylhexahydro-1.3.5-triazine, and acrylamide derivatives of alkylated melamine formaldehyde polymers represented by Formula 4:

(2)

(In Formula 2, each R is independently hydrogen or alkyl having 1 to 10 carbon atoms, such as a methyl group);

(3)

(In Formula 3, each R is independently hydrogen or alkyl having 1 to 10 carbon atoms, such as a methyl group.)

[Chemical Formula 4]

Wherein each R is independently hydrogen or a straight or branched alkyl group of 1 to 10 carbon atoms, at least one R is alkyl, and R 1 is hydrogen or an alkyl group of 1 to 10 carbon atoms, such as a methyl group.

The acrylamide-based crosslinking agent may be in the form of a monomer, oligomer, or polymer.

While not wishing to be bound by any theory, it is believed that the repeating units derived from the crosslinking agent contribute to imparting rigidity to the backbone of the copolymer and maintaining the pore structure.

The weight ratio between the crosslinking agent and the starting material in the mesoporous copolymer may vary depending on the kind of the selected crosslinking agent and the starting material, the desired use of the mesoporous copolymer, the reaction conditions, and the like, but is not particularly limited. The weight ratio of crosslinking agent to starting material may range from about 1000: 1 to about 1: 1000. More specifically, 1,3,5-triacryloylhexahydro 1,3,5-triazine (hereinafter THAT) is selected as a crosslinking agent, and 2-acrylamido-2- is used as a starting material having a reactive functional group. When methylpropanesulfonic acid (ie, compound of formula (II), hereafter AMPS) is selected, the weight ratio between the two may be about 10: 1 to about 1:10. When TAHT and glycidyl methacrylate (ie, compound of formula (IV), hereinafter GMA), respectively, are selected as starting materials having a crosslinking agent and a reactive functional group, the weight ratio between them can be from about 10: 1 to about 1: 1: 1 have. If TAHT and 2-isocyanatoethylmethacrylate (ie, the compound of formula (I), hereinafter MOI) are selected as starting materials having a crosslinking agent and a reactive functional group, respectively, the weight ratio between them is about 10: 1 to about 1: 10 may be.

In some embodiments, the mesoporous copolymer comprising reactive functional groups exhibits substantially no microporosity and has a high specific surface area and low bulk density, including a plurality of pores that are predominantly mesoporous in size. . For example, the mesoporous copolymer may have a mean pore diameter of about 2 nm to about 100 nm, specifically about 5 nm to about 50 nm, more specifically about 5 nm to about 30 nm. And have a BET surface area (SSA) of about 100 m ² / g or more, such as about 200 m ² / g to about 1500 m ² / g, and about 0.8 g / cm ³ or less, such as about 0.01 m ² / g It may have a bulk density of about 0.3 m ² / g and may have a pore volume of about 0.1 m ³ / g to about 10 m ³ / g. However, these values may be adjusted as necessary through the selection of the crosslinking agent and the starting material, the ratio adjustment between the two, and the reaction conditions. Compared to microporous materials which exhibit molecular pore sizes and are used as selective reaction catalysts but have limited accessibility to active sites and material diffusion, crosslinked polymers having multiple mesopores having the properties described above Easy entry and exit of the compound. In addition, in the case of the mesoporous crosslinked polymer, the bulk density is low while the density of the functional group can be adjusted to be high, thereby increasing the number of reactive functional groups present in the polymer per volume, thereby providing a plurality of reaction sites even in a small amount of structure. have. In addition, it has a high specific surface area and can be usefully used for supporting the catalyst or storing gas using physical adsorption. Moreover, since the kind of functional group which can be contained in a polymer varies, different physical properties, such as hydrophilicity-hydrophobicity, can be provided to a polymer.

Since the mesoporous copolymer can form a monolithic structure, it is easy to make a large area in actual application of catalysts and adsorption materials, and is less likely to cause problems caused by swelling (for example, pore blockage). . Thus, the mesoporous copolymer may be characterized by selective removal / purification of impurities using a reaction catalyst (support), liquid phase or gas phase chemical reaction (e.g. acid group reaction or new covalent bond formation reaction), physical / chemical adsorption / It may be advantageously used for transportation.

In particular, the mesoporous copolymer has a light and relatively high flexibility since the entire polymer has an organic skeleton in which organic compounds are linked through covalent bonds based on organic chemical bonds (CC, CO, CN, etc.). In addition, due to the high hydrothermal stability and chemical resistance, it is more stable to moisture and exhibits stability against various metals compared to the mesoporous materials according to the prior art based on metal oxides or organic-inorganic hybrid materials.

Provided according to another embodiment of the present invention, a method for preparing a mesoporous crosslinked copolymer including a reactive functional group,

a) at least one starting material represented by the following formula (1), and C6 to C20 aromatic ring residues, C3 to C12 heteroaromatic ring residues containing a nitrogen atom, and C3 to C12 heteroalicyclics Dissolving an acrylamide-based crosslinking agent having at least one of the ring residues and at least two (alkyl) acryloyl groups or (alkyl) acrylamide groups in a solvent:

[Formula 1]

Wherein R ₁ , A, m, n, and R ₂ are as defined above; And

b) adding, dissolving and heating the radical polymerization initiator to the reaction solution obtained in step a) to form a gel.

The hetero aromatic ring moiety includes a substituted or unsubstituted triazine moiety such as triaminotriazine, and the hetero alicyclic ring moiety includes a substituted or unsubstituted hexahydrotriazine moiety such as hexahydrotriazine.

The method of preparing the mesoporous copolymer may include the steps of c) aging the gel obtained in step b); And d) optionally, replacing the solvent from the gel aged in step c) and optionally drying it.

An example is shown in FIG. 1 to help understand the manufacturing method, but the method is not limited thereto. As illustrated in FIG. 1, the preparation method may consist of a simple sol-gel process that proceeds under relatively mild reaction conditions, thereby providing a desired copolymer in a one-pot / one-step reaction. It can be obtained simply, and phase separation is performed by the formation of a crosslinked gel by polymerization without any other means, and thus a template for forming pores such as a surfactant is not required.

In the above production method, R ₂ , which is a radical polymerizable group of the starting material, and an acrylamide group of the crosslinking agent form a chemical gel which is not dissolved in a solvent even under conditions such as temperature change and pH change by radical initiated polymerization reaction. do. The kind of the solvent for dissolving the starting material and the crosslinking agent is not particularly limited, so that the starting material, the crosslinking agent, the initiator can be dissolved, and the crosslinked polymer produced can be phase separated as the polymerization / crosslinking proceeds. Any solvent to be selected can be appropriately selected. Specific examples of the solvent that can be used include, but are not limited to, amides such as DMF, DMAC, NMP, ethers such as THF, and the like. As the radical polymerization initiator for the polymerization reaction, any initiator capable of generating a radical to initiate polymerization can be used without particular limitation. Examples of initiators that can be used include, but are not limited to, azo compounds such as AIBN, peroxides such as benzoyl peroxide, acetyl peroxide, dilauryl peroxide, ammonium persulfate, and the like. The amount of the initiator is not particularly limited, and may be appropriately selected in consideration of starting materials, types of crosslinking agents, physical properties of desired polymers, and the like. For example, the initiator may be used in an amount of about 0.001 wt% to about 10 wt% based on the sum of the weights of the starting materials and the crosslinking agent, but is not limited thereto. In addition, the heating temperature is not particularly limited, and may be appropriately selected depending on the type of initiator, starting material, and crosslinking agent. For example, the heating temperature is about 30 ℃ to about 150 It may be in the range of ℃, but is not limited thereto. The time for forming the gel is also not particularly limited and may be appropriately selected depending on the type of initiator, starting material and crosslinking agent. For example, the gel formation time is about 0.01 to about 3 hours, but is not limited thereto.

The production method uses an organic compound as a starting material to form a crosslinked polymer via a radical reaction path, so that the desired reactive functional groups present in the starting material remain in their original state after the polymerization reaction and have a nano-sized organic structure. Can be introduced within. Therefore, no additional process such as post-synthesis reforming is required for the introduction of reactive functional groups, thereby reducing manufacturing time and manufacturing cost.

In some embodiments, the gel obtained in step b) is prepared as a wet gel in which the solvent is substituted without additional drying, or dried by various drying methods such as supercritical drying, depending on the field of application thereof. Can be prepared as a porous organic material, such as airgel, zerogel, or the like, which has been removed. As described above, the radically polymerizable group of the starting material, R ₂ , forms a new bond with the acrylamide group of the crosslinking agent or is converted to another functional group, but R _{1, which} is a reactive functional group of the starting material, is the same before and after the polymerization reaction. Since it has a reaction activity, the obtained wet gel or aerogel and the like will contain the reactive functional group as it is.

The aging may be performed under conditions such as atmospheric pressure and gelation reaction temperature, but is not limited thereto.

The solvent for solvent substitution is not particularly limited and may be appropriately selected depending on the kind of polymer prepared. Specific examples of the solvent usable for the solvent substitution include ketones such as acetone, alcohols, ethers, and the like, but are not limited thereto.

The drying method may be appropriately selected so that the pores formed in the crosslinked gel can be maintained even after drying depending on the kind of the polymer prepared, the kind of the solvent contained in the polymer, the temperature, and the like. Specific examples of the drying method that can be used include, but are not limited to, simple drying, supercritical drying, vacuum drying, freeze drying, and the like.

The prepared mesoporous crosslinked copolymers are various reaction catalysts in various fields including petrochemical, fine chemistry, and energy environment fields, for example, acid hydrolysis catalysts, alkylation catalysts, aldolization of biomass such as sugars, Base catalysts for carbonylation, Knoevenagel reactions, catalysts for various condensation reactions such as condensation of acetone and phenol for bisphenol A, various dehydration reaction catalysts such as dehydration of tertiary butyl alcohol, dimerization catalysts , Selective removal / separation / transportation of materials using ester reaction catalysts, etherification catalysts, hydration catalysts, selective hydrogenation catalysts and the like, their support, physical / chemical adsorption or molecular recognition, nanoporous membranes, reaction membranes Its usefulness can be found in gas support (storage / transport / separation) using chemical / physical adsorption, supports for solid reactions, and the like.

Hereinafter, specific embodiments of the present invention will be described. It is to be understood, however, that the embodiments described below are only for illustrative purposes or to illustrate the present invention, and the present invention should not be limited thereby.

[ Example ]

Example  One: TAHT - AMPS  Preparation of Mesoporous Crosslinked Polymer

2.0 g of 1,3,5-triacryloylhexahydro-1,3,5-triazine (hereinafter available from TAHT, Tokyo Chemical Industry Co. Ltd.) and 0.5 g of 2-acrylamido-2 Prepare the reactant solution by dissolving methylpropane sulfonic acid (hereinafter AMPS, available from Aldrich Chemical Co. Ltd.) in 25 ml of dimethylformamide (DMF). To the reactant solution, 0.0125 g of azobisisobutyronitrile (hereinafter referred to as AIBN) is added and dissolved at ambient temperature and the reaction mixture is then heated to 80 ° C. in an oven. Allow the solution to gel at this temperature (in this case, the gelation time is less than or equal to about 5 minutes) and then aged at 80 ° C. for 8 hours. Thereafter, the gel was taken out and washed with acetone to carry out solvent substitution, and the gel thus obtained was dried using supercritical CO ₂ under a temperature of about 40 ° C. and 100 bar, thereby drying TAHT-co-AMPS in monolithic form. Obtain a gel.

Example  2: TAHT - GMA  Preparation of Mesoporous Polymers

Instead of AMPS, except that 0.5 g glycidyl methacrylate (hereafter obtained from GMA, Aldrich Chemical Co. Ltd.) was used TAHT-co-GMA dry gel was prepared in the same manner as in Example 1.

Example  3: TAHT - MOI  Preparation of Mesoporous Polymers

Instead of AMPS, except that 0.5 g of 2-isocyanatoethyl methacrylate (hereinafter obtained from MOI, Showwa Denko KK) was used TAHT-co-MOI dry gel was prepared in the same manner as in Example 1.

Example  4: alkylated melamine formaldehyde copolymer derivatives and AMPS Preparation of Mesoporous Copolymer

Acrylamide derivative of methylated melamine formaldehyde copolymer consisting of repeating units of the following formula (hereinafter PFMFA, 80 wt%, available from Aldrich Chemical Co. Ltd.) 2.5 g and AMPS (obtained from Aldrich Chemical Co. Ltd.) 0.5 Prepare the reactant solution by dissolving g in 24.5 ml of DMF. To the reactant solution, 0.0125 g of AIBN is added to dissolve at ambient temperature and the reaction mixture is then heated to 80 ° C. in an oven. Allow the solution to gel at this temperature (gel time is less than about 5 minutes) and then age at 80 ° C. for 8 hours. Subsequently, the gel was taken out, washed with acetone to carry out solvent substitution, and the monolithic gel thus obtained was dried using supercritical CO ₂ under a temperature of about 40 ° C. and 100 bar to form a methylated melamine formaldehyde copolymer. Obtain PFMFA-co-AMPS dry gel:

Example  5: 1,4- Phenylenediacrylamide - AMPS  Preparation of Mesoporous Polymers

A 1,4-phenylenediacrylamide-AMPS dry gel was prepared in the same manner as in Example 1 except that instead of TAHT, 2.0 g of 1,4-phenylenediacrylamide was used as the crosslinking agent.

Experimental Example  1- Characterization of the prepared crosslinked copolymer

(1) Spectroscopic analysis of copolymers using FT-IR and solid carbon NMR

FT for mesoporous dry gel and TAHT simple polymers (hereinafter referred to as pTAHT) obtained from Examples 1 to 3 to confirm the formation of copolymers of TAHT and AMPS, TAHT and GMA, and TAHT and MOI. Perform FT-IR analysis and solid ¹³ C cross polarization magic angle spinning (CP MAS) NMR analysis using -IR spectrometer and ¹³ C NMR spectrometer and the results are shown in FIGS. 2 and 3 respectively. It was.

As shown in FIG. 2, when compared to the IR spectrum of pTAHT (TAHT in FIG. 2), the obtained dried gels exhibited different characteristic peaks in the IR spectrum. Specifically, TAHT-co-AMPS dried gel 1368 cm For the (in Fig. 2 TcA) ^- In the case of ¹ showed a characteristic peak of the acid from (from FIG. 2, TcG) TAHT-co- GMA dried gel 1187 / 1126 exhibited a characteristic of the epoxy group peak in cm ^-1, 2273cm for (TcM in Fig. 2) TAHT-co-MOI drying ^{gel-exhibited} a characteristic peak for the isocyanate in ^one. From the above results, it can be seen that the reactive functional group derived from the starting material was successfully introduced into the skeleton of the crosslinked copolymer.

On the other hand, as shown in FIG. 3, the solid C NMR spectrum of pTAHT (TAHT in FIG. 3) showed peaks around 207, 174, 128, 57, and 36 ppm, whereas TAHT-co-AMPS of Example 1 (TcA in FIG. 3), TAHT-co-GMA (TcG in FIG. 3) of Example 2, and TAHT-co-MOI (TcM in FIG. 3) of Example 3, respectively, were 27 ppm (in addition to the peak of pTAHT). TAHT-co-AMPS), 45/48 ppm (TAHT-co-MOI), and 45 ppm (TAHT-co-GMA) showed additional peaks. These peaks make it possible to identify the presence of carbon from methyl or methylene attached to oxygen, which is not present in TAHT simple polymers.

(2) SEM analysis

A scanning electron micrograph (SEM) of the monolithic gel prepared in Example 1 is shown in FIG. 4. It can be seen from FIG. 4 that the gel obtained in Example 1 is mesoporous.

(3) N ₂ adsorption-desorption analysis

TAHT-co-AMPS dry gel obtained in Examples 1 to 3 (abbreviated as TcA in FIG. 5), TAHT-co-GMA dry gel (abbreviated as TcG in FIG. 5), TAHT-co-MOI dry N ₂ adsorption-desorption analysis at 77K was performed on the gel (abbreviated as TcM in FIG. 5), and the resulting N ₂ adsorption-desorption isotherm curve is shown in FIG. 5. As can be seen from the curve, the dried gels obtained in Examples 1 to 3 were mainly mesoporous, indicating the presence of larger pores of 50 to 100 nm, and no microporosity was observed.

The morphological properties, surface area, pore volume and pore size of the nanoporous material obtained from these isothermal curves of the samples are summarized in Table 1 below:

a: The weight ratio between TAHT and AMPS is 2: 1, and the weight ratio of TAHT and GMA and TAHT and MOI is 4: 1, respectively.

b: bulk density

c: BET surface area

d: typical pore volume

e: average pore diameter

From the results of spectroscopic analysis, SEM analysis and nitrogen adsorption analysis, it can be seen that a highly functionalized mesoporous organic material was formed via a simple sol-gel process using radical polymerization.

Experimental Example  2- Catalytic Performance Evaluation of Prepared Mesoporous Crosslinked Copolymers

According to the following scheme using TAHT-co-AMPS (2: 1) obtained in Example 1, butanol and 3,4-dihydropyran were left at room temperature for 20 hours to perform an etherification reaction:

The conversion yield was at least 98%.

Experimental Example  3- Amine Adsorption of Prepared Mesoporous Copolymers Performance test

The mesoporous copolymers prepared in Examples 1 to 3 as the adsorption medium were subjected to adsorption tests of CH ₂ (BuNH ₂ ) using trimethylbenzene as the internal standard (conditions: room temperature, stirred for 1 hour). The results are shown in Table 2 below.

Sample Ar-H (TMB) CH ₂ (BuNH ₂ ) NH ₂ adsorption rate standard 1.0 3.81 0% THAT-co-AMPS 1.0 0.36 90.6% THAT-co-GMA 1.0 3.49 8.4% THAT-co-MOI 1.0 3.28 13.9%

Depending on the type of substituent, the adsorption rate of 90.6% for THAT-co-AMPS where the adsorption reaction occurs by acid / base reaction, and THAT-co-GMA and THAT-co-MOI where adsorption reaction occurs by chemical bonding , Adsorption rates of 8.4% and 13.9%, respectively.

From Experimental Examples 2 and 3, it can be seen that the mesoporous crosslinked copolymers prepared in Examples 1 to 3 can be advantageously used as catalysts or adsorption media.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims (20)

Recurring units derived from one or more starting materials represented by Formula 1:
[Chemical Formula 1]

Wherein R ₁ is a reactive functional group that does not participate in a radical reaction, A is a direct bond or an organic moiety as a linker, m and n are each independently an integer of 1 or more, and R ₂ is a radical Polymerizable groups, provided that when m or n is 2 or more, each R ₁ or R ₂ is the same or different; And
Two or more (alkyl) acryloyl groups or one of a C6 to C20 aromatic ring, a C3 to C12 heteroaromatic ring residue comprising a nitrogen atom, and a C3 to C12 heteroalicyclic ring residue comprising a nitrogen atom or ( Repeating unit derived from acrylamide crosslinking agent which has an alkyl) acrylamide group
Mesoporous crosslinked copolymer comprising a. The method of claim 1,
In Formula 1, R ₁ is a hydroxy group, alkoxy group, isocyanate group, amine group, sulfonic acid group, carboxyl group, pyridine group, epoxy group or silane functional group, phosphoric acid group, urea group, sulfonyl urea group and aziridine group May be selected, R ₂ may be a (alkyl) acrylate group, a (alkyl) acrylamide group, or a vinyl group, and A is a direct bond or a substituted or unsubstituted linear or branched alkylene group of C1 to C30. Of amine groups, ether groups, carbonyl groups, ester groups, substituted or unsubstituted C6 to C20 aromatic ring residues, and substituted or unsubstituted C3 to C20, including substituted or unsubstituted C1 to C30 alkylene residues. A mesoporous crosslinked copolymer which is an organic moiety comprising at least one of alicyclic ring moieties . The method of claim 1,
The starting material is a mesoporous crosslinked copolymer which is a compound selected from the group consisting of the following formulas (I) to (X):

In formula (VII), X is SO ₃ Na, NH ₂ , or CO ₂ H, and m, n, 1 in formulas (IX) and (X) are each from 1 to 10000 . The method of claim 1,
The heteroaromatic ring moiety comprises a substituted or unsubstituted triazine moiety, and the heteroalicyclic ring moiety comprises a substituted or unsubstituted hexahydrotriazine moiety. The method of claim 1,
The crosslinking agent is phenylenedi (alkyl) acrylamide, 1,3,5-tri (alkyl) acryloylhexahydro-1,3,5-triazine represented by formula (3), and alkylated melamine represented by formula (4). Mesoporous crosslinked copolymers selected from the group consisting of (alkyl) acrylamide derivatives of formaldehyde polymers:
(3)

In Formula 3, R is each independently hydrogen or alkyl having 1 to 10 carbon atoms;
[Chemical Formula 4]

Wherein R is each independently hydrogen or a linear or branched alkyl group of 1 to 10 carbon atoms, at least one of R is alkyl, and R 1 is hydrogen or an alkyl group of 1 to 10 carbon atoms. The method of claim 1,
Mesoporous crosslinked copolymer in monolithic form containing mesopores. The method of claim 1,
In the mesoporous crosslinked copolymer, the weight ratio between the crosslinking agent and the starting material is 1000: 1 to 1: 1000 mesoporous crosslinked copolymer. The method of claim 1,
The mesoporous copolymer is a mesoporous copolymer having an average pore diameter of 2 nm to 100 nm. The method of claim 1,
The mesoporous copolymer has at least one of a BET surface area of at least 100 m ² / g, a bulk density of at most 0.8 g / cm ³ , and a pore volume of 0.1 m ³ / g to 10 m ³ / g. Mesoporous copolymer. A process for preparing a mesoporous crosslinked copolymer having a reactive functional group, comprising the following steps:
a) at least one starting material represented by formula (1):
[Chemical Formula 1]

Wherein R ₁ is a reactive functional group that does not participate in radical reactions, A is a direct bond or an organic moiety as a linker, m and n are each independently an integer of at least 1, and R ₂ is a radical polymerizable group, m or when n is 2 or more, each R ₁ or R ₂ is the same or different; And
Two or more (alkyl) acryloyl groups or one of a C6 to C20 aromatic ring, a C3 to C12 heteroaromatic ring residue comprising a nitrogen atom, and a C3 to C12 heteroalicyclic ring residue comprising a nitrogen atom or ( Dissolving an acrylamide-based crosslinking agent having an alkyl) acrylamide group in a solvent; And
b) adding a radical polymerization initiator to the reaction solution obtained in step a), dissolving and heating to form a mesoporous crosslinked copolymer gel. The method of claim 10,
In Formula 1, R ₁ is a hydroxy group, alkoxy group, isocyanate group, amine group, sulfonic acid group, carboxyl group, pyridine group, epoxy group, silane-based functional group, phosphoric acid group, urea group, sulfonylurea group, and aziridine group May be selected, R ₂ may be a (alkyl) acrylate group, a (alkyl) acrylamide group, or a vinyl group, and A is a direct bond or a substituted or unsubstituted straight or branched alkylene group of C1 to C30. , Substituted or unsubstituted amine group including C1 to C30 alkylene residue, ether group, carbonyl group, ester group, substituted or unsubstituted C6 to C20 aromatic ring residue, and substituted or unsubstituted C3 to C20 A process for producing a mesoporous crosslinked copolymer having a reactive functional group, which is an organic moiety comprising at least one of alicyclic ring moieties. The method of claim 10,
The heteroaromatic ring moiety comprises a substituted or unsubstituted triazine moiety, and the hetero alicyclic ring moiety comprises a substituted or unsubstituted hexahydrotriazine moiety, preparing a mesoporous crosslinked copolymer having a reactive functional group. Way. The method of claim 10,
The crosslinking agent is phenylenedi (alkyl) acrylamide, 1,3,5-tri (alkyl) acryloylhexahydro-1,3,5-triazine represented by formula (3), and alkylated melamine represented by formula (4). Process for preparing a mesoporous crosslinked copolymer having a reactive functional group, selected from the group consisting of acrylamide derivatives of formaldehyde polymers:
(3)

Wherein each R is independently hydrogen or alkyl of 1 to 10 carbon atoms
[Chemical Formula 4]

Wherein each R is independently hydrogen or an alkyl group having 1 to 10 carbon atoms, straight or branched, at least one R is alkyl, and each R 1 is independently hydrogen or alkyl of 1 to 10 carbon atoms. The method of claim 10,
c) aging the gel obtained in step b); And d) optionally drying the gel aged in step c). The method of claim 10,
The crosslinking agent: the weight ratio of the starting material is, 1000: 1 to 1: 1000 method of producing a mesoporous crosslinked copolymer having a reactive functional group. The method of claim 10,
The gel has a monolith (monolith) form containing mesopores, method of producing a mesoporous copolymer having a reactive functional group. The method of claim 10,
Wherein said gel exhibits mesoporosity and has an average pore diameter of 2 nm to 100 nm. The method of claim 10,
The gel has mesoporous with reactive functional groups having at least one of a BET surface area of at least 100 m ² / g, a bulk density of at most 0.8 g / cm ³ , and a pore volume of 0.1 m ³ / g to 10 m ³ / g. Method of Making Copolymers. A reaction catalyst comprising the mesoporous crosslinked copolymer according to any one of claims 1 to 9. Adsorption material comprising the mesoporous crosslinked copolymer according to any one of claims 1 to 9.

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