KR102142344B1 - Method for manufacturing solid crosslinked poymer including polyethyleneimine - Google Patents

Abstract

A method for producing a solid phase crosslinked polymer containing polyethyleneimine is provided. The manufacturing method comprises the steps of obtaining a mixture by mixing polyhedral oligomeric silsesquioxane (POSS) containing polyethyleneimine and an epoxy group, and through the ring-opening polymerization of the amino group and epoxy group of the polyethyleneimine It includes the step of obtaining a polymer from.

Description

Manufacturing method of solid phase crosslinked polymer containing polyethyleneimine{METHOD FOR MANUFACTURING SOLID CROSSLINKED POYMER INCLUDING POLYETHYLENEIMINE}

The present invention relates to a method for producing a solid phase crosslinked polymer containing polyethyleneimine.

Many studies have been conducted on the reduction and removal of greenhouse gases, especially carbon dioxide, which have been identified as the cause of abnormal climates. Carbon dioxide is a major cause of global warming and accounts for 80% of greenhouse gases. Among various technologies to reduce greenhouse gas, carbon capture and storage (CCS) refers to a technology that prevents emission into the atmosphere by adsorbing/absorbing and absorbing/recycling carbon dioxide generated in the combustion process of materials. .

Typical examples of the study on the adsorption and removal of carbon dioxide include a wet method using ammonia water and a liquid small molecule amine as an adsorbent, and a dry method using solid particles such as zeolite and activated carbon as an adsorbent.

In general, the adsorption chemical reaction between amine and carbon dioxide proceeds as in the following reaction formulas (1) to (3), but the reaction progress rate varies depending on the type of amine.

In the primary amine or secondary amine capable of providing a hydrogen cation, 2 mol of amine absorbs 1 mol of carbon dioxide to produce carbamate (see Scheme (1) below), and the resulting carbamate is again hydrolyzed. It is converted to bicarbonate (see Scheme (3) below).

_{CO 2 + 2R 2 NH → R} 2 NCOO - + R 2 NH 2 + < Reaction Formula (1)>

_{CO 2 + R 2 NH + H} 2 O → HCO 3 - + R 2 NH 2 + < Reaction Scheme 2>

^{_{R 2 NCOO - + H 2 O}} → HCO 3 - + R 2 NH 2 < Reaction Formula (3)>

Polyethyleneimine has a myriad of amino groups (-NH ₂ ) capable of chemically adsorbing carbon dioxide in a molecule, but since it is a viscous liquid material, it does not have a certain form, so the adsorption efficiency of carbon dioxide is very low and chemically unstable due to a large number of amino groups. Therefore, it is easily oxidized and lacks thermal stability to adsorb carbon dioxide in a high temperature environment.

The present invention seeks to solve the above-mentioned problems of polyethyleneimine through a crosslinking reaction between an organic-inorganic hybrid material having an epoxy group and polyethyleneimine.

The problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

The method for preparing a solid phase crosslinked polymer containing polyethyleneimine according to the present invention comprises the steps of obtaining a mixture by mixing polyethyleneimine and a polyhedral oligomeric silsesquioxane (POSS) containing an epoxy group and the polyethyleneimine And obtaining a polymerization product from the mixture through the ring-opening polymerization reaction of an amino group and an epoxy group.

The weight ratio (A:B) of the polyethyleneimine (A) and the POSS (B) containing the epoxy group may be 30:70 to 95:5.

As the content of the POSS having the epoxy group increases, the stability improves, but the carbon dioxide adsorption performance decreases.

In order to improve stability without significantly reducing the carbon dioxide adsorption performance, the weight ratio (A:B) of the polyethyleneimine (A) and the POSS (B) containing the epoxy group is preferably 70:30 to 95:5. .

The polyethyleneimine may be a compound represented by Formula 1 below.

<Formula 1>

In Chemical Formula 1, n is a natural number of 2 or more and 1500 or less.

POSS containing the epoxy group may be a compound represented by the following formula (2).

<Formula 2>

In Chemical Formula 2, R is hydrogen, alkyl having 1 to 10 carbon atoms containing an epoxy group, and alkoxy having 1 to 10 carbon atoms containing an epoxy group, and at least two of the R's have 1 to 10 carbon atoms containing an epoxy group. Alkyl having 1 to 10 carbon atoms containing an alkyl or epoxy group. For example, at least two of the Rs may be composed of glycidoxypropyl.

Specific details of other embodiments are included in the detailed description and drawings.

The manufacturing method according to the present invention improves chemical stability, thermal stability and mechanical properties compared to liquid polyethyleneimine without compromising the excellent carbon dioxide adsorption capacity of polyethyleneimine by crosslinking the chains of polyethyleneimine using POSS containing an epoxy group. Solid phase crosslinked polymer.

The effects according to the present invention are not limited by the contents exemplified above, and more various effects are included in the present specification.

1 is an FT-IR spectrum of test samples and comparative samples.
2 is an SEM image of a comparative sample.
3 to 6 are SEM images of test samples.
FIG. 7 is a table showing the composition ratio of each test sample and comparison sample measured using EDX.
8 is a TGA spectrum of test samples.
9 is a TGA spectrum of comparative samples.
10 is a DTG spectrum of test samples.
11 is an enlarged view of a box portion of FIG. 10.
12 is a DTG spectrum of comparative samples.
13 is an enlarged view of a box portion of FIG. 12.
14 and 15 are graphs comparing the carbon dioxide adsorption performance of test samples and comparative samples.

Advantages and features of the present invention, and methods for achieving them will be clarified through embodiments described below in detail with reference to the accompanying drawings. It should be noted that the accompanying drawings are only for facilitating understanding of the spirit of the technology disclosed in this specification, and should not be interpreted as limiting the spirit of the technology by the accompanying drawings.

In addition, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms, and only the embodiments allow the disclosure of the present invention to be complete, and common knowledge in the technical field to which the present invention pertains. It is provided to fully inform the holder of the scope of the invention, and the invention is only defined by the scope of the claims.

In addition, in describing the technology disclosed in the present specification, when it is determined that a detailed description of a related known technology may obscure the gist of the technology disclosed in this specification, the detailed description will be omitted.

Throughout this specification, when a part "includes" or "haves" a certain component, it does not exclude other components unless specifically stated otherwise, and may further include other components. it means.

In addition, in this specification, "A to B" means that it is in the range of A or more and B or less, and "A or more and less than B" means that it is in the range of A or more and less than B, and "A to B to less than B" Means that it is in the range of A to B or less.

The method for preparing a solid-phase crosslinked polymer containing polyethyleneimine according to the present invention (hereinafter referred to as a'manufacturing method') is a polyhedral oligomeric silsesquioxane having a polyethylenimine and an epoxy group. And mixing to obtain a mixture, and obtaining a polymerization product from the mixture through the ring-opening polymerization reaction of the amino group and the epoxy group of the polyethyleneimine.

POSS having an epoxy group is a hybrid material having a Si-O-Si skeleton and excellent mechanical properties and thermal stability, which can improve the mechanical properties and thermal stability of the polymer, and a crosslinking agent that crosslinks the chains of polyethyleneimine through a ring-opening polymerization reaction. Can play a role.

The ring-opening polymerization reaction is a typical nucleophilic substitution reaction, and a ring of the epoxy group is opened by the ring-opening polymerization reaction as shown in the following reaction formula (4), whereby a carbon-nitrogen bond is formed between POSS having an epoxy group and polyethyleneimine.

<반응식 (4) >

<Reaction Scheme (4)>

The manufacturing method of the present invention can obtain a three-dimensional crosslinking system in which chains of polyethyleneimine are crosslinked with POSS simply and easily by the one-step ring opening polymerization reaction described above.

The weight ratio (A:B) of the polyethyleneimine (A) and the POSS (B) containing the epoxy group may be 30:70 to 95:5.

As the content of the POSS having the epoxy group increases, the stability improves, but the carbon dioxide adsorption performance decreases.

In order to improve stability without significantly reducing the carbon dioxide adsorption performance, the weight ratio (A:B) of the polyethyleneimine (A) and the POSS (B) containing the epoxy group is preferably 70:30 to 95:5. .

Examples of polyethyleneimine include compounds represented by the following formula (1).

<Formula 1>

In Chemical Formula 1, n is a natural number of 2 or more and 1500 or less.

Examples of POSS having an epoxy group include compounds represented by the following Chemical Formula 2.

<Formula 2>

In Chemical Formula 2, R is hydrogen, an alkyl group having 1 to 10 carbon atoms having an epoxy group, and an alkoxy group having 1 to 10 carbon atoms having an epoxy group, wherein at least two of the Rs have 1 to 1 carbon atoms having an epoxy group. It may be an alkyl group having 10 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

Examples of the R include glycidoxypropyl, and at least two of R may be composed of glycidoxypropyl.

Hereinafter, effects of the present invention will be described in detail based on Examples and Comparative Examples.

<Preparation of test samples according to Examples 1 to 5>

In a 50 mL flask, polyethyleneimine (PEI, Polyethylenimine), methanol, and glycidyl-POSS having a weight average molecular weight of 10.000 were added at various ratios as shown in Table 1 below, and the mixture was sufficiently mixed using a mechanical stirrer. Subsequently, the sufficiently mixed solution was loaded into a desired mold, and a ring-opening polymerization reaction was sufficiently performed at 80 °C for 24 hours.

The product obtained through the ring-opening polymerization panel was removed from the mold, washed several times with methanol to remove impurities and unreacted materials, and then dried to obtain a test sample.

Reaction Scheme (5) below shows a reaction process for obtaining a three-dimensional crosslinking system in which PEI chains are crosslinked with GP through ring-opening polymerization (ROP) of PEI and Glycidyl-POSS (GP).

<Reaction formula (5)>

<Preparation of comparative samples according to Comparative Examples 1 to 2>

Instead of glycidyl-POSS, 1,4-Butanediol diglycidyl ether (BDE) represented by the following Chemical Formula 3 was used, and polyethylenimine (PEI) and methanol, 1,4-Butanediol diglycidyl ether (BDE) as shown in Table 2 below. ) Except for mixing, a comparative sample was obtained in the same manner as in Example.

<Formula 3>

PGP 0.5, PGP 1, PGP 3, PGP 5, PGP 7, PBDE 0.5, PBDE 1 described in the remarks column of Table 1 and Table 2 are Examples 1 to 5, Comparative Examples 1 Reference numerals used to denote 2 to 2.

PEI GP Methanol Remark Example 1 95 g 5 g 9 g PGP 0.5 Example 2 90 g 10 g 9 g PGP 1 Example 3 70 g 30 g 9 g PGP 3 Example 4 50 g 50 g 9 g PGP 5 Example 5 30 g 70 g 9 g PGP 7

PEI BDE Methanol Remark Comparative Example 1 95 g 5 g 9 g PBDE 0.5 Comparative Example 2 90 g 10 g 9 g PBDE 1

The structure, morphology, stability, etc. of samples obtained by using FT-IR, SEM (Scanning Electron Microscope), EDX (Energy Dispersive X-ray Spectroscopy), TGA (Thermogravimetric Analyzer), and DTG (differential thermogravimetry) were tested.

In addition, carbon dioxide adsorption performance of samples obtained using a mixed gas consisting of 85 vol% N ₂ and 15 vol% CO ₂ was compared.

<Judgment of synthesis using FR-IR>

Figure 1 shows the FT-IR spectrum of the test samples (PGP 1, PGP 3, PGP 5, PGP 7) and the comparative sample (PBDE 1). 1, the inventors of the present application were able to confirm that all of the test samples (PGP1, PGP3, PGP5, PGP7) and the comparative sample (PBDE1) were successfully synthesized.

Referring to FIG. 1, it can be seen that the peak of the primary amine seen in the PEI decreases through the reaction with the epoxy group and the peak of the secondary amine increases. As the epoxides of GP and BDE were opened by the primary amine of PEI, the peak was reduced, and the -OH peak was generated as a wide peak due to the ring-opening reaction. In addition, it was confirmed that Si-O-Si peaks appearing from the GP also appeared in PGP synthesized at various ratios.

<Morphology measurement using SEM>

FIG. 2 is an SEM image of a comparative sample (PBDE 1), and FIGS. 3 to 6 are SEM images of test samples (PGP 1, PGP 3, PGP 5, PGP 7).

3 to 6, as the proportion of GP increases, the crosslinked structures have a morphology in which the surface area is increased by having particulate and fragmentary characteristics.

2 and 3, when GP and BDE are cross-linked with PEI at the same ratio, PBDE 1 has a morphology that has less surface area and less graininess than PGP 1. Test samples (PGP 1, PGP 3, PGP 5, PGP 7) are expected to adsorb large amounts of carbon dioxide more efficiently than pure PEI and comparative samples (PBDE 1) through increased surface area.

<Measurement of composition ratio by element using EDX>

7 shows the composition ratio of elements cross-linked using EDX (PGP 1, PGP 3, PGP 5, PGP 7, PBDE 1).

Referring to FIG. 7, when the proportion of GP increases, the amount of Si and O elements increases, and when the proportion of PEI decreases, the proportion of C and N elements tends to decrease. The thermal stability, chemical stability and mechanical properties of the test samples (PGP 1, PGP 3, PGP 5, PGP 7) can be controlled by adjusting the GP ratio and the PEI ratio.

<Measurement of thermal stability using TGA>

8 shows the TGA spectrum of the test samples (PGP 0.5, PGP 1, PGP 3, PGP 5, PGP 7), and FIG. 9 shows the TGA spectrum of the comparative samples (PBDE 0.5, PBDE 1). .

Table 3 below shows the TGA measurement results of the samples, and T- _d , 10% is the temperature when 10 wt% of the material participating in the analysis is lost.

T _d ,10%(℃) Residue at 400℃(%) Char Yield at 800℃(%) PEI 323 6.5 0.5 PGP 0.5 301 13.4 3.75 PGP 1 317 26.75 9.03 PGP 3 340 50.8 15.02 PGP 5 336 61.51 22.4 PGP 7 379 79.3 34.67 PBDE 0.5 296 2.92 - PBDE 1 313 4.3 -

Referring to FIG. 8 and Table 3, test samples (PGP 0.5, PGP 1, PGP 3, PGP 5, PGP 7) remain solvent (methanol) used for synthesis and purification, and T _d , 10% is pure PEI It is lower, but it can be seen that the thermal stability is significantly increased based on 400°C.

On the other hand, referring to Figure 9 and Table 3, it can be seen that the comparative samples (PBDE 0.5, PBDE 1) have similar thermal properties to pure PEI.

In summary, PEI (PGP 0.5, PGP 1, PGP 3, PGP 5, PGP 7) cross-linked with POSS has superior thermal stability compared to PEI (PBDE 0.5, PBDE 1) cross-linked with BDE, so this excellent thermal stability It is expected that PEI, which is crosslinked with POSS based on, can exert sufficient function as a carbon dioxide adsorbent even in a high temperature environment.

<Confirmation of decomposition speed using DTG>

10 shows the DTG spectrum of the test samples (PGP 0.5, PGP 1, PGP 3, PGP 5, PGP 7), and FIG. 11 is an enlarged view of the box portion of FIG. 10.

FIG. 12 shows the DTG spectrum of the comparative samples (PBDE 0.5, PBDE 1), and FIG. 13 is an enlarged view of the box portion of FIG. 12.

DTG is the first derivative of the TGA curve for time and temperature, and the decomposition rate increases as it goes negative.

10 and 11, it can be seen that as the proportion of GP of the crosslinked material increases, the decomposition rate decreases even at a higher temperature, and thus the thermal stability increases as the proportion of GP of the crosslinked material increases. On the other hand, referring to FIGS. 12 and 13, the PEI cross-linked with BDE ((PBDE 0.5, PBDE 1) is at a lower temperature than the PEI cross-linked with POSS (PGP 0.5, PGP 1, PGP 3, PGP 5, PGP 7). The decomposition speed is fast.

<Confirmation of CO2 adsorption performance>

14 and 15 show graphs comparing carbon dioxide adsorption performance of test samples (PGP 0.5, PGP 1, PGP 3, PGP 5, PGP 7) and comparative samples (PBDE 0.5, PBDE 1).

Table 4 summarizes the measurement results of carbon dioxide absorption performance of comparative samples (PBDE 0.5, PBDE 1) and test samples (PGP 0.5, PGP 1, PGP 3, PGP 5, PGP 7).

Carbon dioxide absorption performance (mmol/g) PGP 0.5 1.002 PGP 1 0.91 PGP 3 0.56 PGP 5 0.39 PGP 7 0.05 PBDE 0.5 0.4617 PBDE 1 0.67

As the proportion of GP increases, the amount of amine groups capable of adsorbing carbon dioxide of PEI (PGP 0.5, PGP 1, PGP 3, PGP 5, PGP 7) crosslinked with POSS decreases, and the adsorption performance decreases gradually. Can.

When comparing the carbon dioxide adsorption performance over time of the test samples having the same ratio (PGP 0.5, PGP 1) and the comparative samples (PBDE 0.5, PBDE 1), they all form a network by crosslinking, but are tested compared to the comparative samples. The carbon dioxide adsorption performance of the samples is excellent, and the test samples have a significant effect on absorbing carbon dioxide even when the proportion of GP is less than 10%.

This is because when the PEI is cured using BDE, the viscosity characteristic, which is a problem of the PEI, has not been solved, and as a result, comparative samples show a low amount of carbon dioxide adsorption.

It has been proven that POSS solves the viscosity problem of PEI compared to BDE, increases the surface area and facilitates the reaction with carbon dioxide.

As a result of analyzing the synthesized structures using various analyzers, as the proportion of POSS increased, thermal stability and the particle size of the structure were solved to solve the PEI disadvantage, but the comparative material BDE was synthesized in the same proportion as POSS, but the relative crosslinking degree Decreased and showed similar properties to thermally pure PEI, and it was found that the absolute amount of carbon dioxide adsorption decreased as the ratio of PEI decreased in both structures.

Through the above results, POSS-based structures are considered to be more efficient materials in thermal stability and carbon dioxide adsorption characteristics than BDE-based structures.

The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and may be manufactured in various different forms, and having ordinary knowledge in the technical field to which the present invention pertains. It will be understood that a person can be implemented in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (4)

Mixing polyhedral oligomeric silsesquioxane (POSS) containing polyethyleneimine and an epoxy group to obtain a mixture; And
Including the step of obtaining a polymerization product from the mixture through the ring-opening polymerization of the amino group and the epoxy group of the polyethyleneimine;
The weight ratio of the polyethyleneimine and the POSS containing the epoxy group is 70:30 to 95:5
Method for preparing a solid phase crosslinked polymer: delete According to claim 1,
The polyethyleneimine is a compound represented by the following formula (1),
POSS containing the epoxy group is a compound represented by the following formula (2)
Method for preparing a solid phase crosslinked polymer:
<Formula 1>

In Chemical Formula 1, n is a natural number of 2 or more and 1500 or less.
<Formula 2>

In Chemical Formula 2,
R is one of hydrogen, an alkyl having 1 to 10 carbons containing an epoxy group, and an alkoxy having 1 to 10 carbons containing an epoxy group, and at least two of the Rs contain an alkyl or epoxy group having 1 to 10 carbons containing an epoxy group. It is an alkoxy having 1 to 10 carbon atoms. According to claim 3,
In Formula 2, at least two of the R is glycidoxypropyl solid phase crosslinked polymer production method.

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