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Scientific Reports Volume 6, Article Number: 24038 (2016) Cite this article

As a simple and environmentally friendly method, the direct polymerization of CO2 and diols is expected to replace traditional processes that use high-cost and/or hazardous reagents (such as phosgene, carbon monoxide, and epoxides). However, due to the direct polymerization, it is still There is no report on the direct polymerization method. The inertness of CO2 and the severe equilibrium limit of the reaction. Here, we first confirmed the direct copolymerization of CO2 and diol using CeO2 catalyst and 2-cyanopyridine promoter, providing high diol-based yield (up to 99%) and selectivity (up to >99%) to provide alternate low Polymer. This catalyst system is suitable for various diols including linear C4-C10 α,ω-diols to provide high yields of corresponding oligomers, which are well known by CO2 and cyclic ether copolymerization and ring-opening polymerization. The method cannot be obtained. Cyclic carbonate. Due to the simplicity of diol modification, this process provides us with a simple method for synthesizing multifunctional polycarbonate from various diols and CO2.

From the perspective of environment and green chemistry, the direct conversion of carbon dioxide into valuable chemicals is one of the hottest topics 1, 2, 3, 4, 5, 6, 7. CO2 conversion can be divided into two main methods, reductive conversion and non-reductive conversion1,4,5. The non-reductive conversion of CO2 includes the reaction of CO2 with compounds with polar functional groups such as alcohols and amines, providing a variety of important chemicals, such as urea, carbamate, carbonate and polycarbonate. Compared with reducing, Because of the low energy input, it is very promising. Transformation. However, because CO2 has a very strong double bond, it is very stable, so a sophisticated catalyst system is needed to activate CO2 and reagents. As we all know, carbonic anhydrase is an ideal catalyst system for the non-reductive conversion of CO2, which can significantly accelerate the reaction of CO2 and H2O to produce bicarbonate and protons (approximately 106 times compared with non-catalyst) 8,9,10,11,12 In this catalyst system, Zn2 ions and histidine residues activate H2O to generate active hydroxides on Zn2 ​​ions (cooperation of Lewis acid and Lewis base), and CO2 is hydrophobic by three valine residues. The bag is guided to the vicinity of the hydroxide (substrate concentration), forming a configuration that is conducive to the reaction. As for the artificial catalyst, since the size of the artificial catalyst is smaller than that of the enzyme, it is quite difficult to reach a level equivalent to that of the enzyme. Therefore, it is necessary to create delicate and precise artificial catalysts that can simultaneously activate CO2 and reagents near each other.

CeO2 is widely used in the field of catalysts and biochemistry due to its unique acid-base and redox properties13,14 and has recently attracted attention in low-temperature (≤473 K) 15,16,17 liquid phase organic synthesis,18,19 ,20,21. In particular, it is reported that CeO2 plays a vital role in the non-reductive conversion of CO2 to organic carbonates, carbamates and urea using alcohols or amines 22,23,24,25,26,27, 28, 29, 30, 31, 32, although these reactions have a common equilibrium limitation. Recently, we have found that the dehydration condensation of alcohol and CO2 catalyzed by CeO2 and the hydration of 2-cyanopyridine catalyzed by CeO2 to form picolinamide can form the corresponding organic carbonate 33,34,35 in high yield. In the reaction of CH3OH, CO2 and 2-cyanopyridine, the methanol-based yield of DMC reached 94%, while the equilibrium yield of DMC in the reaction of CH3OH and CO2 without 2-cyanopyridine was less than 1%. This is the first report on the stoichiometric conversion of alcohol and CO2 to the corresponding carbonate. We also proved that CO2 can be strongly adsorbed and activated on the acid-base sites of CeO233, 34, 35, and methanol can be activated synergistically by CeO2 and 2-cyanopyridine at the interface between CeO2 and 2-cyanopyridine 36 This has some common points to the above enzyme catalytic system (mainly the coordination of Lewis acid and Lewis base with substrate concentration). In addition, Urakawa and colleagues also applied this catalyst system to DMC synthesis under a wide range of CO2 pressures (1-30 MPa) in a fixed-bed reactor, achieving a higher reaction rate than batch operation37. These results motivate us to apply this catalyst system to the direct synthesis of polycarbonate from CO2 and diol.

As a common material for engineering plastics, polycarbonate has a market size of 290 million tons per year in 2009, and it is expected to increase by about 4 to 6% annually by 202038 and 39. Therefore, polycarbonate is one of the most promising CO2 targets, which will help to incorporate large amounts of CO2 into chemicals due to the large market size. The industry has produced polycarbonate by using phosgene as a carbonyl source, but phosgene is highly toxic and the process produces a large amount of salt through neutralization. In order to overcome these shortcomings, methods using organic carbonates as carbonyl groups have been developed, such as the condensation of diols and organic carbonates 40, 41, 42 and the ring-opening polymerization of cyclic carbonates 43, 44, 45, 46, 47 ( figure 1). However, these processes have similar problems with the phosgene process, because the organic carbonate substrate in these processes is usually synthesized by the reaction of phosgene with the corresponding alcohol or epoxide, and no alternative environmentally friendly organic carbonic acid has been established. Ester synthesis process. As for the process of using CO2 as a carbonyl source, the copolymerization of cyclic ether and CO2 has been studied in depth (Figure 1) (selected reviews 48,49,50,51 and selected recent papers 52,53,54,55,56 ,57,58,59,60,61,62,63,64). Epoxides and oxetanes have been used as starting materials; however, reports of the copolymerization of CO2 with five-membered or larger cyclic ethers have not been reported at all because such cyclic ethers are difficult to prepare due to low stability. On the other hand, the direct polymerization of diol and CO2 through dehydration condensation will enable the synthesis of polycarbonates with longer alkyl chains (Figure 1, this work). However, the dehydration condensation of diol and CO2 is severely restricted by the reaction equilibrium. For example, it is well known that based on 1,2-propanediol, the equilibrium yield of propylene carbonate from 1,2-propanediol and CO2 is estimated to be lower than 2e. Regarding the direct synthesis of polycarbonate from α,ω-diols and CO2, as far as we know, there are no reports on catalytic and non-catalytic synthesis methods, although the use of K2CO3 to convert CO2, diols and dihalides into polycarbonate 66 .

Here, we proved that the combination of CeO2 catalyst and 2-cyanopyridine promoter is effective for the direct copolymerization of diol and CO2. This is the first report on the direct synthesis of oligomers from CO2 and glycol catalysis.

First, various metal oxides and 2-cyanopyridine were used to study the polymerization reaction of CO2 and 1,4-butanediol (Table 1). 2-cyanopyridine was chosen as the dehydrating agent because 2-cyanopyridine is more suitable for hydration than CeO233, 34, 35, 67, and 68. The reaction was carried out in an autoclave reactor containing metal oxide (0.17 g), 1,4-butanediol (10 mmol), 2-cyanopyridine (100 mmol) and CO2 (5.0 MPa) at 403 K. The calculated conversion and selectivity are based on 1,4-butanediol. The detailed data for the conversion of 2-cyanopyridine is shown in Supplementary Table S1. No oligomer product was obtained in the absence of a metal oxide catalyst (Table 1, entry 13). CeO2 provides oligomers and a small amount of 4-hydroxybutyl picolinate with a yield of 97% (Mn = 1070, dispersion (Mw/Mn) = 1.33), which is composed of 2-cyanopyridine and 1,4-butane Diol production (Table 1, entry 1)) and the Mn of the oligomer corresponds to an oligomer formed from eight CO2 and eight 1,4-butanediol. MALDI-TOF mass spectrometry revealed alternating oligomers formed by CO2 and 1,4-butanediol (Figure 2), and confirmed that no ether bonds were formed. In addition, 2-pyridinecarboxamide was selectively produced by reacting 2-cyanopyridine with H2O produced by the copolymerization of CO2 and 1,4-butanediol (Supplementary Table S1). On the other hand, the conversion rate of other metal oxides is lower than CeO2, and there are no oligomers (Table 1, entries 3-12). Others include dimers, trimers or diesters produced from 2-cyanopyridine and 1,4-butanediol. Therefore, among the metal oxides tested, CeO2 is the only active metal oxide that reacts with 2-cyanopyridine as a dehydrating agent. It should be noted that CeO2 alone does not provide oligomers without 2-cyanopyridine (not shown). Considering this result, the combination of CeO2 and 2-cyanopyridine is essential for the formation of 1,4-butanediol and CO2 oligomers. We first demonstrated the direct copolymerization of CO2 and 1,4-butanediol using a combination of CeO2 catalyst and 2-cyanopyridine promoter. In addition, the reusability of CeO2 catalyst was also studied. CeO2 is easily recovered from the reaction mixture by decantation. The collected catalyst is washed with methanol and then calcined at 873 K for 3 hours, and then the recovered CeO2 is used in the next reaction. CeO2 can be reused without significantly reducing activity and selectivity (Table 1, entry 2). XRD and BET analysis confirmed that the structure of CeO2 did not change during the reusability test (Supplementary Figure S1). In addition, the dissolved amount of Ce in the filtrate is lower than the detection level of ICP-AES (<0.1%), which indicates that CeO2 acts as a true heterogeneous catalyst in this reaction.

MALDI-TOF mass spectra of CO2 and 1,4-butanediol products using CeO2 and 2-cyanopyridine.

2-cyanopyridine reacts with one mole of H2O to form 2-pyridinecarboxamide, indicating that when 10 mmol 1,4-butanediol is used, theoretically 10 mmol 2-cyanopyridine is required to remove all 1,4-butanediol Conversion of alcohols to corresponding oligomers. The effect of the amount of 2-cyanopyridine was studied using CeO2 catalyst (Table 2, detailed data of 2-cyanopyridine conversion are shown in Supplementary Table S2). 10 mmol and greater than 10 mmol of 2-cyanopyridine provide almost the same conversion and Mn (Table 2, entries 2-6), although 5 mmol of 2-cyanopyridine is ineffective because the amount of 2-cyanopyridine is more than theoretical Value a small amount (table 2, entry 1). Therefore, an equivalent amount of 2-cyanopyridine is sufficient to form oligomers from 1,4-butanediol and CO2.

From an environmental and economic point of view, low CO 2 pressure is preferable. The effect of CO2 pressure was studied using CeO2 catalyst and 2-cyanopyridine accelerator (Table 3, detailed data of 2-cyanopyridine conversion are shown in Supplementary Table S3). This reaction can obtain oligomers in good yield even at a low CO2 pressure of 0.5 MPa (Table 3, entry 1), but the conversion rate and Mn gradually decrease with the decrease of CO2 pressure. This result provides the possibility of reaction under low CO2 pressure.

The time course of the copolymerization of CO2 and 1,4-butanediol was studied using CeO2 catalyst and 2-cyanopyridine accelerator (Figure 3, detailed data is shown in Supplementary Table S4 and Supplementary Figures S2 and S3). The reaction proceeded rapidly, reaching a conversion rate of 99% within one hour, and maintaining a high selectivity to oligomers (≥97%) within a short reaction time, which strongly indicates that oligomers are not formed by carbonic acid Produced from tetramethylene ester, the corresponding cyclic carbonate. On the other hand, Mn increased to 8 hours with the reaction time, but gradually decreased when the reaction time exceeded 8 hours. The dispersion degree also increased to about 1.3 within 1 hour, and gradually increased over 1 hour. The decrease in Mn and the increase in dispersibility are attributable to the degradation of oligomers and/or the intramolecular termination caused by the nucleophilic attack of the polymer terminal OH groups, which is called biting back 69,70.

The time course of direct polymerization of 1,4-butanediol and CO2 using CeO2 catalyst and 2-cyanopyridine.

(a) Conversion rate and selectivity (•: conversion rate, ○: selectivity to oligomers, ▵: selectivity to 4-hydroxybutyl picolinate. (b) Mn and Mw/Mn (⋄: Mn , ♦: Mw/Mn). Reaction conditions: CeO2 0.17 g, 1,4-butanediol 10 mmol, 2-cyanopyridine 100 mmol, CO2 5 MPa (at room temperature), 403 K.

Finally, the range of diols was studied in the copolymerization of CO2 and diols using CeO2 catalyst and 2-cyanopyridine promoter (Table 4, detailed data of 2-cyanopyridine conversion are shown in Supplementary Table S5). Linear C4-C10 α,ω-diols are converted into corresponding oligomers in good yield. In the case of C5-C10 diols, no corresponding cyclic carbonates were observed, which supports the direct dehydration condensation of diols and CO2 to occur in this reaction system. Even if any diol is used, the average number of repeating units of these copolymers is 7-8. 1,4-cyclohexanedimethanol and 1,4-benzenedimethanol are diols with rigid structure, which are converted into corresponding copolymers, but their reactivity and Mn are lower than linear alkyl diols. In order to examine the influence of the position of the OH group, a combination of CeO2 catalyst and 2-cyanopyridine promoter was applied to 1,5-hexanediol with one primary and one secondary OH group, and one with two secondary OH groups. 2,5-hexanediol and 2,5-dimethyl-2,5-hexanediol with two tertiary OH groups. 1,5-hexanediol shows lower conversion rate, selectivity and Mn than 1,6-hexanediol with two primary OH groups. 2,5-hexanediol exhibits lower conversion rate, selectivity and Mn than 1,5-hexanediol. In the case of 2,5-dimethyl-2,5-hexanediol, the corresponding oligomer was not obtained. Therefore, the steric hindrance around the OH group greatly reduces the reactivity of the substrate.

The proposed reaction mechanism is shown in Figure 4. Based on previous reports on the synthesis of carbonates from alcohols and CO2 on CeO2 catalysts, the reaction started with (i) the adsorption of diols on the CeO2 surface to form alkoxide products. (ii) CO2 inserts some alkoxide types to provide some carbonate types. (iii) Oxygen anions in alkoxides nucleophilically attack carbonates, and the corresponding carbonates are obtained from 1,4-butanediol and H2O. (iv) Remove the generated H2O by hydrating 2-cyanopyridine to 2-pyridinecarboxamide on CeO233, 34, 35, 67. (v) Finally, the produced carbonate is further reacted with CO2 1,4-butanediol or the produced oligomer to obtain polytetramethylene carbonate. Among these reaction steps, step (iv) is very important in polycarbonate synthesis, which will transfer the reaction to the product side by removing H2O from the reaction medium.

The reaction mechanism of forming oligomers from 1,4-butanediol and CO2 using CeO2 catalyst and 2-cyanopyridine is proposed.

In summary, we first demonstrated the direct copolymerization of CO2 and glycol using a combination of CeO2 catalyst and 2-cyanopyridine promoter. Various diols including α, ω-diols with long alkyl chains can be converted into corresponding oligomers, which are not possible with conventional methods of cyclic carbonate, epoxide or oxetane acquired. This catalyst system will not only open up a new era in polymer chemistry, especially polycarbonate synthesis, but also have a significant impact on the conversion of CO2.

The CeO2 catalyst was prepared by calcining CeO2-HS (Daiichi Kigenso, Japan. CeO2 purity: 99.97%) in air at 873 K for 3 h. The specific surface area of ​​CeO2 (BET method) is 84 m2/G. All chemicals used in organic reactions are commercially available and can be used without further purification. Other metal oxides are commercially available or synthesized by precipitation: ZrO2 (Daiichi Kigenso Kogyo Co. Ltd., Zr(OH)4 calcined in air at 873 K for 3 hours), MgO (Ube Industries, Ltd., MgO 500A , 873 K, 3 h), TiO2 (Nippon Aerosil Co. Ltd., P-25), γ-Al2O3 (Nippon Aerosil), ZnO (FINEX-50, Sakai Chemical Industry Co.,Ltd), SiO2 (Fuji Silysia) Chemical Ltd., 773 K, 1 h), Nb2O5 (Companhia Brasileira de Metalurgia e Mineracao (CBMM), Nb2O5∙nH2O calcined at 773 K for 3 hours). Y2O3, La2O3 and Pr6O11 are prepared by precipitation method. Y(NO3)3∙nH2O (Wako Pure Chemical Industries Ltd., >99.9%), La(NO3)3∙6H2O (Wako Pure Chemical Industries Ltd., >99.9%) and Pr(NO3)3∙nH2O (Wako Pure Chemical Industries Ltd., >99.9%) ) Chemical Industries Ltd., >99.5%) is used as a precursor. The precursor (25g) was dissolved in water (100ml) and NH3aq (1M) was added dropwise with stirring until the pH of the solution became 10, resulting in precipitation. The precipitate was filtered and washed with water, then dried at 383 K overnight (12 hours), and calcined at 873 K (673 K for La2O3) in air for 3 hours.

All reactions were carried out in an autoclave reactor with an internal volume of 190 mL. The standard procedure for the direct polymerization of CO2 and 1,4-butanediol using the combined catalyst of CeO2 and 2-cyanopyridine is as follows: CeO2 (0.17 g, 1 mmol), 1,4-butanediol 0.90 g (10 mmol) and 10.4 g (100 mmol) of 2-cyanopyridine was put into the autoclave together with the rotator, and then the reactor was purged 3 times with 1 MPa CO 2 (Shimakyu Co. Ltd., >99.5%). At room temperature, CO2 is used to pressurize the autoclave to the required pressure (usually 5.0 MPa), and then the autoclave is heated to 433 K, where the CO2 pressure is about 12 MPa. The mixture was continuously stirred during the reaction. After the reaction time, the reactor was cooled to room temperature in a water bath. THF (20 ml) was added as a solvent to the liquid phase, and 1-hexanol (~0.2 ml) was added as an internal standard substance for quantitative analysis. The reactor was washed with THF and the liquid used in the washing was added to the reaction mixture. The amount of 2-cyanopyridine and 2-cyanopyridine products (such as 2-pyridinecarboxamide and 4-hydroxybutylpicolinate) was measured by gas chromatography equipped with FID (Shimadzu GC-2014) using CP/Sil 5 CB for analysis. Since the generated oligomers are decomposed by heating, an HPLC (Shimazu Prominence) equipped with an RI detector (RID-10A) is used. A Pheny-Hexyl Luna column (Phenomenex, particle size 5 μm, 250 mm × 4.6 mm) is used. Conditions: Developing solvent, H2O/CH3OH = 70/30, 0.5 ml/min, 313 K). Since the produced oligomer was precipitated by adding a developing solvent (about 20-fold dilution), the precipitated oligomer was removed by filtration before analysis by HPLC. This filtration operation is performed at least twice until no precipitation is observed. The qualitative analysis of the product was performed by a gas chromatograph equipped with a quadrupole mass spectrometer (GC-MS, Shimazu QP5050) using the same capillary column and nuclear magnetic resonance (Bruker, AV400). The oligomerization product was analyzed by MALDI-TOF quality (Shimazu AXIMA-CFR Plus) using bisanthranol and NaBr as the matrix and ionizer, respectively, and using size exclusion chromatography (SEC, Shimazu Prominence) with an RI detector (RID-10A) ) For analysis Shodex high performance liquid chromatography column KF-805L. The developing agent is THF (Wako Pure Chemical Industries, >99.5%).

The conversion rate and selectivity are calculated by the following equations (Equations 1, 2, 3).

The amount of oligomer is determined by subtracting the amount of ester produced from the amount of diol reacted. Products for which the SEC has not observed a signal are assigned to other products.

The surface area of ​​CeO 2 is measured by the BET method (N 2 adsorption) using Gemini (Micromeritics). X-ray diffraction (XRD) patterns are recorded using MiniFlex 600 and Cu Kα (40 kV, 15 mA) radiation. The amount of metal eluted into the reaction solution was analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES, Thermo Fisher Scientific iCAP 6500).

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This work was partially supported by the ENEOS Hydrogen Trust Fund and partially supported by JST and PRESTO. MALDI-TOF mass spectrometry analysis is carried out by the instrument analysis team, especially by Ms. Mana Nemoto from Tohoku University.

Graduate School of Engineering, Tohoku University, Aoba 6-6-07, Aramaki, Aoba-ku, 980-8579, Sendai, Japan

Masazumi Tamura, Kazuki Ito, Masayoshi Honda, Yoshinao Nakagawa, Keiichi Tomishige

JST, PRESTO, 4-1-8, Honcho, Kawaguchi, 332-0012, Saitama, Japan

Department of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, 12-1 Ichigaya-Funagawara, Shinjuku, 162-0826, Tokyo, Japan

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MT and KT conceived the concept and guided the project. IK, MT and HM conducted experiments. MT, YN and HS discussed the experiment and results and prepared the manuscript.

The author declares that there are no competing economic interests.

This work has been licensed under the Creative Commons Attribution 4.0 International License Agreement. The images or other third-party materials in this article are included in the Creative Commons license of the article, unless otherwise stated in the credit line; if the material is not included under the Creative Commons license, the user will need permission from the license holder to copy The material. To view a copy of this license, please visit http://creativecommons.org/licenses/by/4.0/

Tamura, M., Ito, K., Honda, M. etc. Direct copolymerization of CO2 and glycol. Scientific Report 6, 24038 (2016). https://doi.org/10.1038/srep24038

DOI: https://doi.org/10.1038/srep24038

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