KR20100067593A - An efficient synthetic route for highly active catalysts for co2/epoxide copolymerization - Google Patents

Abstract

PURPOSE: An efficient synthetic method of a highly active catalyst for carbon dioxide/epoxide copolymerization is provided to manufacture a phenol derivative in one step from a conventional same starting material and to reduce a manufacturing cost using an ortho-cresol as a solvent without inputting additional solvent. CONSTITUTION: A compound is marked as a chemical formula 1. In the chemical formula 1, A^1 - A^4 are straight-chain or branched chain alkylene of C2~C20 or cycloalkylene of C3~C20. R^1 is a first or secondary alkyl with C1~C20 and R^2 - R^4 are selected from an alkyl group with C1~C20 and an aryl group with C6~C30. Q is diradical for connecting two nitrogen atoms.

Description

An efficient synthetic route for highly active catalysts for CO2 / epoxide copolymerization

The present invention relates to a novel process for preparing a polycarbonate from an epoxide compound and carbon dioxide, a catalyst prepared through the process, and a process for producing a polycarbonate using the catalyst.

Aliphatic polycarbonates are biodegradable polymers, for example, useful materials for packaging or coatings. The method of preparing polycarbonate from epoxide compound and carbon dioxide is environmentally friendly in that it does not use toxic compound, phosgene, and inexpensively obtains carbon dioxide.

Since the 1960s, many researchers have developed various types of catalysts for producing polycarbonates from epoxide compounds and carbon dioxide. Recently, the investigator has studied a high activity synthesized from a Salen [Salen: ([H ₂ Salen = N , N ' -bis (3,5-dialkylsalicylidene) -1,2-ethylenediamine] -type ligand containing quaternary ammonium salts. , Highly Selective Catalyst [Seoul, Korea Patent Registration 10-0853358 (Registration Date: 2008.08.13); Lee, Fyeol, Sujith S, Eun-Kyung No, Min Jae-Ki, Republic of Korea Patent Application 10-2008-0015454 ;; S. Lee, Sujith S, No Eun Kyung, Jae Jae Ki, PCT / KR2008 / 002453 (filed April 30, 2008); Eun Kyung Noh, Sung Jae Na, Sujith S, Sang-Wook Kim, and Bun Yeoul Lee * J. Am . Chem . Soc . 2007 , 129 , 8082-8083 (2007.07.04); Sujith S, Jae Ki Min, Jong Eon Seong, Sung Jea Na, and Bun Yeoul Lee, Angew . Chem . Int . Ed . , 2008 , 47, 7306-7309. (2008.09.08)]. The catalyst disclosed by the present inventors exhibits high activity, high selectivity, can produce copolymers having high molecular weight, and can be polymerized even at high temperatures, thereby allowing commercial application. In addition, since the quaternary ammonium salt is included in the ligand, the catalyst can be easily separated from the copolymer after the carbon dioxide / epoxide copolymerization reaction and reused.

In addition, the present inventors closely analyze the structure of a catalyst which exhibits particularly high activity and high selectivity compared with other catalyst groups of the patent, and the structure is such that the oxygen atom is not coordinated with the nitrogen atom of Salen-ligand. It was revealed that it had a unique structure that was not known previously, and patented a new type of catalyst group therefrom (Korean Patent Application No. 10-2008-0074435, filed on July 30, 2008).

All of the above patents have the characteristics prepared from the ligand containing the quaternary ammonium salt, the synthesis method of the catalyst among them is shown in Scheme 1 below. As shown in Scheme 1, a high activity catalyst has to go through several stages of organic synthesis, and these complex stages of manufacturing are obstacles to commercialization of polycarbonate.

Scheme 1

Synthesis yield from step 1 to step 5 to 9 is almost 100%, so that the reaction can proceed to the next step without particular purification of the product obtained after each step reaction is not a big problem. The process in the synthetic route that is a problem to get the compound 5 from compound 1 that is, step 5 in step 1. In the first bromination reaction, Br _2, which is harmful to the human body, must be used, and by-products are purified by column chromatography using silica gel. Column chromatography purification using silica gel is not suitable when a large amount of silica and a solvent are required to produce organic materials in large quantities. The second stage is to protect the alcohol group, and the yield is high (about 90%), but the next step is to use a high purity starting material in the three stage reaction. Purification of the product by chromatography is necessary. The most problematic step is three steps. The reason for using butyllithium is to proceed the reaction without air contact and to use a solvent that is thoroughly purified and does not contain water and oxygen. In addition, the yield is low (about 74%), and the product is purified by column chromatography using silica gel or the like. Step 4 is a hydrogenation reaction using Pd / C, in which the alcohol group at the benzyl position is reduced, as well as deprotection of the tetrahydropyranyl (THP) group to give compound 5 . In this reaction, some impurities are generated, and after the reaction, a process of purifying the product by column chromatography using silica gel is required.

In order to solve the problems as described above, the first technical problem of the present invention is to prepare a phenol derivative substituted with a tertiary alkyl at 4 carbon by using a phenolic compound (phenolic compounds) substituted with an alkyl group at carbon 2 as a starting material It is to provide a method for producing in one step reaction, and a phenol derivative prepared by the above method without going through several steps.

A second technical problem of the present invention is to provide a novel ligand prepared using the phenol derivative as a starting material, and a cobalt complex compound prepared from the ligand.

The third technical problem of the present invention is to provide a polycarbonate production method characterized in that the cobalt complex compound as a catalyst to copolymerize the epoxide compound and carbon dioxide.

In order to achieve the first object of the present invention, the present invention provides a phenol derivative of the formula (5), and a phenol compound of the formula (6) and a tertiary alcohol compound of the formula (7) It provides a method for producing a phenol derivative.

[Chemical Formula 5]

[Formula 6]

[Formula 7]

In Formulas 5 to 7, A ⁹ and A ¹⁰ are independently straight or branched chain (C 2 -C 20) alkylene or (C 3 -C 20) cycloalkylene.

The R ¹¹ is a primary or secondary (C1 ~ C20) alkyl, in the case of tertiary alkyl, the reaction yield is reduced by the production of by-products by various side reactions, and a process for purifying it is required, and cobalt prepared therefrom In the case of a complex compound, it is preferable that the structure is different and its activity is low, thus being primary or secondary alkyl. More specifically, they are primary or secondary (C1-C7) alkyl.

R ¹² is selected from (C 1 -C 20) alkyl or (C 6 -C 30) aryl, and more specifically (C 1 -C 7) alkyl.

X ³ and X ⁴ are independently selected from Cl or Br.

In the present invention, aryl may include an aromatic ring such as phenyl, naphthyl, anthracenyl, biphenyl, and the like, and a carbon atom of the carbon aromatic ring may be substituted with a hetero atom such as N, O, or S.

As the acid catalyst, AlCl ₃ may be used, or inorganic acids such as phosphoric acid and sulfuric acid may be used, and a solid acid catalyst may be used to reuse the catalyst after the reaction. Examples of the solid acid catalyst include Nafion NR 50, Amberlyst-15, H-ZSM 5, H-Beta, HNbMoO ₆ , and the like (Kazunari Domen et al., J. AM. CHEM. SOC. 2008, 130 , 7230). -7231).

The tertiary alcohol compound of Chemical Formula 7 may be prepared by various organic reactions, and Scheme 2 below provides an example thereof.

Scheme 2

In order to achieve the second object of the present invention, there is provided a novel ligand compound of the formula (1) prepared by using a phenol derivative as a starting material.

[Formula 1]

In Formula 1, A ¹ to A ⁴ are independently a linear or branched (C 2 to C 20) alkylene group or a (C 3 to C 20) cycloalkylene group, preferably propylene.

In Formula 1, R ¹ is a primary or secondary (C1 ~ C20) alkyl group, in the case of tertiary alkyl, the reaction yield is reduced by the generation of by-products by various side reactions and a process for purifying the same is required. In the case of the prepared cobalt complex compound, it is preferable that the structure is different and the activity is low, so that it is primary or secondary alkyl. More specifically, they are primary or secondary (C1-C7) alkyl, most preferably methyl.

In Chemical Formula 1, R ² to R ⁴ are independently selected from (C 1 -C 20) alkyl or (C 6 -C 30) aryl groups, and more specifically R ² to R ⁴ are independently selected from (C 1 -C 7) alkyl. Most preferably R ² is methyl and R ³ and R ⁴ are butyl.

In Formula 1, Q is a diradical bond to connect two nitrogen atoms, specifically (C6 ~ C30) arylene, (C1 ~ C20) alkylene, (C2 ~ C20) alkenylene, (C2 ~ C20 Alkynylene, (C3-C20) cycloalkylene or fused (C3-C20) cycloalkylene or the arylene, alkylene, alkenylene, alkynylene, cycloalkylene or fused cycloalkylene is halogen It may be further substituted with a substituent selected from an atom, a (C1-C7) alkyl, a (C6-C30) aryl or a nitro group, or may include one or more heteroatoms selected from oxygen, sulfur and nitrogen. More specifically Q is selected from ethylene, trans-1.2-cyclohexylene, or 1,2-phenylene.

In Formula 1 Z ^- is in or at the same time, each independently, a halogen anion, BF ₄ ^-, ClO ₄ ^-, NO ₃ ^-, or PF ₆ ^- is independently selected from a ^- is selected from, more specifically, iodide or BF ₄ do.

More preferably, the ligand compound of Formula 1 may be a ligand compound of Formula 2 below.

[Formula 2]

In Formula 2, m and n are independently an integer of 1 to 20, preferably 2.

In Chemical Formula 2, R ¹ is a primary or secondary (C 1 ~ C 20) alkyl, in the case of tertiary alkyl, the reaction yield is reduced by the generation of by-products by various side reactions and a process for purifying the same is required. In the case of the prepared cobalt complex compound, it is preferable that the structure is different and the activity is low, so that it is primary or secondary alkyl. More specifically, they are primary or secondary (C1-C7) alkyl, most preferably methyl.

In Chemical Formula 2, R ² to R ⁴ are independently selected from (C 1 -C 20) alkyl or (C 6 -C 30) aryl group, and more specifically R ² to R ⁴ are independently selected from (C 1 -C 7) alkyl. Most preferably R ² is methyl and R ³ and R ⁴ are butyl.

In Formula 2, Q is a diradical bond to connect two nitrogen atoms, specifically (C6 ~ C30) arylene, (C1 ~ C20) alkylene, (C2 ~ C20) alkenylene, (C2 ~ C20 Alkynylene, (C3-C20) cycloalkylene or fused (C3-C20) cycloalkylene or the arylene, alkylene, alkenylene, alkynylene, cycloalkylene or fused cycloalkylene is halogen It may be further substituted with a substituent selected from an atom, a (C1-C7) alkyl, a (C6-C30) aryl or a nitro group, or may include one or more heteroatoms selected from oxygen, sulfur and nitrogen. More specifically Q is selected from ethylene, trans-1.2-cyclohexylene, or 1,2-phenylene.

In the formula 2 Z ^- is in or at the same time, each independently, a halogen anion, BF ₄ ^-, ClO ₄ ^-, NO ₃ ^-, or PF ₆ ^- is independently selected from a ^- is selected from, more specifically, iodide or BF ₄ do.

In order to achieve the second object of the present invention, there is provided a cobalt complex of formula (3) prepared from formula (1) or formula (2).

(3)

In Formula 3, A ⁵ to A ⁸ are independently straight or branched (C 2 -C 20) alkylene or (C 3 -C 20) cycloalkylene, preferably independently straight or branched (C 2 -C 6) Alkylene, most preferably propylene.

In Formula 3, R ⁵ is primary or secondary (C 1 -C 20) alkyl, preferably primary or secondary (C 1 -C 7) alkyl, most preferably methyl.

In Chemical Formula 3, R ⁶ to R ⁸ are independently (C 1 -C 20) alkyl or (C 6 -C 30) aryl, preferably independently (C 1 -C 7) alkyl, most preferably R ⁶ is methyl , R ⁷ and R ⁸ are butyl.

In Chemical Formula 3, Q is a diradical bond to connect two nitrogen atoms, specifically, (C6 ~ C30) arylene, (C1 ~ C20) alkylene, (C2 ~ C20) alkenylene, (C2 ~ C20) alkynylene, (C3-C20) cycloalkylene or fused (C3-C20) cycloalkylene or the arylene, alkylene, alkenylene, alkynylene, cycloalkylene or fused cycloalkylene It may be further substituted with a substituent selected from a halogen atom, (C1 ~ C7) alkyl, (C6 ~ C30) aryl or nitro group, or may include one or more hetero atoms selected from oxygen, sulfur and nitrogen. More specifically Q is selected from ethylene, trans-1.2-cyclohexylene, or 1,2-phenylene.

In Chemical Formula 3, Z ¹ to Z ⁵ are independently a halogen anion; BF ₄ ^-; ClO ₄ ^-; NO ₃ ^-; PF ₆ ^-; HCO ₃ ^-; (C6-C30) aryloxy anion with or without halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C1-C20) carboxylic acid anion; (C1-C20) alkoxy anion; (C1-C20) alkylcarbonate anion; (C1-C20) alkyl sulfonate anion; (C1-C20) alkyl amido (amide) anion; Z ¹ to Z ⁴ selected from (C 1 to C 20) alkylcarbamate anions and coordinated to cobalt Some of them may be decoordinated. More specifically, Z ¹ to Z ⁵ is 2,4-dinitro phenolate or BF ₄ ^- is independently selected from.

More preferably, the cobalt complex of Formula 3 may be a cobalt complex of Formula 4.

[Formula 4]

In Formula 4, p and q are independently an integer of 1 to 20, preferably an integer of 1 to 5, most preferably 2.

In Formula 4, R ⁵ is primary or secondary (C 1 -C 20) alkyl, preferably primary or secondary (C 1 -C 7) alkyl, most preferably methyl.

In Chemical Formula 4, R ⁶ to R ⁸ are independently (C 1 -C 20) alkyl or (C 6 -C 30) aryl, preferably independently (C 1 -C 7) alkyl, most preferably R ⁶ is methyl , R ⁷ and R ⁸ are butyl.

In Chemical Formula 4, Q is a diradical bond to connect two nitrogen atoms, and specifically, (C6 ~ C30) arylene, (C1 ~ C20) alkylene, (C2 ~ C20) alkenylene, (C2 ~ C20) alkynylene, (C3-C20) cycloalkylene or fused (C3-C20) cycloalkylene or the arylene, alkylene, alkenylene, alkynylene, cycloalkylene or fused cycloalkylene It may be further substituted with a substituent selected from a halogen atom, (C1 ~ C7) alkyl, (C6 ~ C30) aryl or nitro group, or may include one or more hetero atoms selected from oxygen, sulfur and nitrogen. More specifically Q is selected from ethylene, trans-1.2-cyclohexylene, or 1,2-phenylene.

In Chemical Formula 4, Z ¹ to Z ⁵ are independently a halogen anion; BF ₄ ^-; ClO ₄ ^-; NO ₃ ^-; PF ₆ ^-; HCO ₃ ^-; (C6-C30) aryloxy anion with or without halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C1-C20) carboxylic acid anion; (C1-C20) alkoxy anion; (C1-C20) alkylcarbonate anion; (C1-C20) alkyl sulfonate anion; (C1-C20) alkyl amido (amide) anion; Z ¹ to Z ⁴ selected from (C 1 to C 20) alkylcarbamate anions and coordinated to cobalt Some of them may be decoordinated. More specifically, Z ¹ to Z ⁵ is 2,4-dinitro phenolate or BF ₄ ^- is independently selected from.

In order to achieve the third object of the present invention, there is provided a method for producing a polycarbonate comprising the step of copolymerizing an epoxide compound and carbon dioxide using the cobalt complex of formula (3) or (4) as a catalyst.

The epoxide compound is (C2 ~ C20) alkylene oxide unsubstituted or substituted with halogen or alkoxy; (C4-C20) cycloalkylene oxide unsubstituted or substituted with halogen or alkoxy; And it may be selected from the group consisting of (C8 ~ C20) styrene oxide unsubstituted or substituted with halogen, alkoxy, alkyl or aryl. Specifically, the alkoxy includes alkyloxy, aryloxy, aralkyloxy, and the like, and the aryloxy includes phenoxy, biphenyloxy, naphthyloxy, and the like. The alkoxy, alkyl and aryl may have a substituent selected from a halogen element or an alkoxy group.

Specific examples of the epoxide compound include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, butadiene monoxide , 1,2-epoxide-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxidenorbornene, limonene oxide, Dieldrin, 2,3-epoxidepropylbenzene, styrene oxide, phenylpropylene oxide, stilbene jade Id, chlorostilbene oxide, dichlorostilbene oxide, 1,2-epoxy-3-phenoxypropane, benzyloxymethyl oxirane, glycidyl-methylphenyl ether, chlorophenyl-2,3-epoxidepropyl ether, epoxy Propyl methoxyphenyl ether biphenyl glycidyl ether, glycidyl naphthyl ether, and the like.

Epoxide compounds may be used for polymerization using an organic solvent as a reaction medium, which may include aliphatic hydrocarbons such as pentane, octane, decane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, chloromethane, methylene Chloride, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, ethylchloride, trichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, One or a combination of two or more of halogenated hydrocarbons such as 1-chloro-2-methylpropane, chlorobenzene and bromobenzene may be used. More preferably, bulk polymerization using the monomer itself as a solvent can be performed.

The molar ratio of epoxide compound to catalyst, ie the epoxide compound: catalyst molar ratio, can be used at 1,000 to 1,000,000, preferably at 50,000 to 200,000.

At this time, the conversion rate of the catalyst, that is, the number of moles of the epoxide compound consumed per mole of cobalt complex compound per hour can be realized more than 500 turnover / hr.

The pressure of carbon dioxide in the copolymerization step may be up to 100 atm at normal pressure, preferably 30 atm at 5 atm.

In the copolymerization step, the polymerization temperature may be from 20 ° C to 120 ° C, preferably 50 ° C to 90 ° C.

As a method of polymerizing a polycarbonate, it can manufacture by a batch polymerization method, a semi-batch polymerization method, or a continuous polymerization method. In the case of using a batch or semibatch polymerization method, the reaction time can be 1 to 24 hours, preferably 1.5 to 4 hours. It is preferable that the average residence time of the catalyst in the case of using the continuous polymerization method is also 1.5 to 4 hours.

According to the present invention, a polycarbonate having a number average molecular weight (M _n ) having a molecular weight of 5,000 to 1,000,000 and a molecular weight distribution (ie, M _w / M _n ) having a value of 1.05 to 4.0 can be produced. Here, M _n means the number average molecular weight measured by GPC by correcting the polystyrene of a single molecular weight distribution with a standard material, the molecular weight distribution M _w / M _n value is the weight average molecular weight and number average specified by GPC by the same method The ratio between the molecular weights.

The polycarbonate polymers produced are composed of at least 80% carbonate bonds and often at least 95% carbonate bonds. Polycarbonates prepared according to the invention are polymers which are easy to decompose and are free of residues and soot upon combustion, for example, materials useful as packaging materials, insulation materials or coating materials.

The conventional synthetic method is to prepare a phenol derivative from ortho-cresol in five stages, Br ₂ , which is harmful to the human body, butyllithium sensitive to air and moisture, and purification of the product by column chromatography using silica gel at every stage. There is a big problem in mass production.

The novel preparation method according to the present invention can prepare a similar phenol derivative from the same starting material in one step, ortho-cresol remaining after the reaction by using the starting material ortho-cresol as a solvent without adding additional solvent. Silver can be reused by vacuum distillation, making the production cost low. In addition, by-products are not produced, allowing the product to be used in the next step without further purification, which allows for production in large quantities.

In addition, according to the present invention, the manufacturing process of the cobalt complex prepared by using the phenol derivative is simplified by one step, and the manufacturing cost of the cobalt complex is significantly reduced. There is an advantage.

The present invention will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.

Example 1

1,7- Dichloro -4- Methylheptane -4-ol (1,7- Dichloro -4- methylheptan -4- ol ) Synthesis

Dissolve 1,7-dichloroheptan-4-one (17.40 g, 95.04 mmol) in diethyl ether (285 mL) under nitrogen atmosphere. After the temperature was lowered to −78 ° C., a 1.5 M diethyl ether MeLi solution (80.97 g, 142.56 mmol) was slowly added dropwise with a syringe under a nitrogen atmosphere. After stirring at −78 ° C. for 2 hours, water (170 mL) is added to terminate the reaction. Extract three times with diethyl ether (300 mL) to collect only the organic layer. Water was removed with anhydrous magnesium sulfate, filtered and the solvent was removed using a rotary vacuum concentrator to obtain a reaction product. The yield is 17.99 g (95%) and the product obtained can be used for the next reaction without further purification.

¹ H NMR (CDCl ₃ ): δ. 3.59 (t, J = 6.4 Hz, 4H, CH ₂ Cl), 1.90-1.86 (m, 4H, CH ₂ ), 1.64-1.60 (m, 4H, CH ₂ ), 1.23 (s, 3H, CH ₃ ) ppm . ¹³ C { ¹ H} NMR (CDCl ₃ ): δ. 72.32, 45.88, 39.51, 27.60, 27.23

Compound 5 'Synthesis

Ortho-cresol (78.17 g, 722.82 mmol), 1,7-dichloro-4-methylheptan-4-ol (17.99 g, 90.35 mmol), AlCl ₃ under a nitrogen atmosphere (13.25 g, 99.39 mmol) are mixed in a round bottom flask and stirred overnight. Diethyl ether (500 mL) and water (300 mL) were added to terminate the reaction. The organic layer was received, and the water layer was extracted three more times with diethyl ether (300 mL) to collect the organic layers. Water is removed with anhydrous magnesium sulfate, filtered and the solvent is removed using a rotary vacuum concentrator. The obtained compound was vacuum reduced (2 mmHg) in an 85 degreeC oil bath, and the ortho-cresol thrown in in excess was removed. The compound remaining in the flask was pure enough to be used for the next reaction without further purification and the yield was 25.40 g (97%).

¹ H NMR (CDCl ₃ ): δ. 7.01 (d, J = 2.0 Hz, 1H, m -H), 6.97 (dd, J = 8.0 Hz, 2.0 Hz, 1H, m -H), 6.72 (d, J = 8.0 Hz, 1H, o -H) , 4.85 (s, 1H, OH), 3.45 (t, J = 6.4 Hz, 4H, CH ₂ Cl), 2.27 (s, 3H, CH ₃ ), 1.86-1.44 (m, 8H, CH ₂ ), 1.30 ( s, 3H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ. 151.79, 138.67, 129.06, 125.02, 123.45, 114.85, 46.20, 41.12, 39.95, 28.09, 24.22, 16.58

[Example 2]

Compound 6 'Synthesis

Compound 5 ' (25.40 g, 87.83 mmol) is dissolved in tetrahydrofuran (650 mL) under nitrogen atmosphere. Paraformaldehyde (10.55 g, 351.32 mmol), magnesium chloride (33.52 g, 351.32 mmol) and triethylamine (37.31 g, 368.89 mmol) were added to the flask in order under a nitrogen atmosphere, and the reflux condenser was connected for 5 hours. Stir at reflux. The solvent was removed using a rotary vacuum concentrator and methylene chloride (500 mL) and water (300 mL) were added. Filtration with celite removes the suspended solids to obtain a methylene chloride layer. The water layer is extracted three more times with 300 mL of methylene chloride and all organic layers are collected. Water was removed with anhydrous magnesium sulfate, filtered and the solvent was removed using a rotary vacuum concentrator to obtain an oily compound. The vacuum pump is used to remove some of the remaining triethylamine. NMR analysis of the obtained compound showed a high purity, which was used without further purification in the next reaction. Yield 26.75 g (96%).

¹ H NMR (CDCl ₃ ): δ. 11.14 (s, 1H, OH), 9.87 (s, 1H, CH = O), 7.33 (d, J = 2.4 Hz, 1H, m -H), 7.26 (d, J = 2.4 Hz, 1H, m -H ), 3.47 (t, J = 6.4 Hz, 4H, CH ₂ Cl), 2.30 (s, 3H, CH ₃ ), 1.90-1.40 (m, 8H, CH ₂ ), 1.35 (s, 3H, CH ₃ ) ppm . ¹³ C { ¹ H} NMR (CDCl ₃ ): δ. 196.87, 158.22, 137.56, 136.11, 128.91, 119.69, 45.88, 40.67, 39.98, 27.96, 24.06, 15.81

Compound 7 'Synthesis

Compound 6 ' (26.75 g, 84.32 mmol) is dissolved in acetonitrile (107 mL). Sodium iodide (126.39 g, 843.18 mmol) was added thereto, followed by a reflux condenser, refluxed and stirred overnight. After cooling to room temperature, 300 mL of water are added. Extract three times with diethyl ether (300 mL) to collect only the organic layer. Anhydrous magnesium sulfate was added to remove water from the organic layer, followed by filtration and removal of the solvent using a rotary vacuum concentrator. Pure compound was obtained by silica gel column chromatography using hexane-toluene mixture (5: 1) as a developing solution (22.17 g, 83%).

¹ H NMR (CDCl ₃ ): δ. 11.14 (s, 1H, OH), 9.87 (s, 1H, CH = O), 7.33 (d, J = 2.4 Hz, 1H, m -H), 7.25 (d, J = 2.4 Hz, 1H, m -H ), 3.14-3.09 (m, 4H, CH ₂ I), 2.30 (s, 3H, CH ₃ ), 1.87-1.43 (m, 8H, CH ₂ ), 1.34 (s, 3H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ. 196.85, 158.20, 137.50, 136.09, 128.85, 126.93, 119.62, 44.28, 39.95, 28.66, 24.16, 15.81, 7.99

Compound 8 'Synthesis

Dissolve compound 7 ' (8.56 g, 17.01 mmol) in methylene chloride (97 mL) under a nitrogen atmosphere. Add (±) trans-1,2-diaminocyclohexane (0.97 g, 8.50 mmol) and stir overnight. Removal of the solvent in vacuo afforded a pure compound (9.00 g, 98%).

¹ H NMR (CDCl ₃ ): δ. 13.48 (s, 1H, OH), 8.31 (s, 1H, CH = N), 7.04 (d, J = 1.6 Hz, 1H, m -H), 6.91 (d, J = 1.6 Hz, 1H, m -H ), 3.38-3.35 (m, 1H, cyclohexyl-CH), 3.08-3.03 (m, 4H, CH ₂ I), 2.25 (s, 3H, CH ₃ ), 1.96-1.89 (m, 2H, cyclohexyl-CH ₂ ), 1.96-1.43 (m, 10H, cyclohexyl-CH ₂ and CH ₂ ), 1.26 (s, 3H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ. 165.01, 157.31, 136.12, 131.35, 126.93, 125.54, 117.67, 72.94, 44.47, 39.79, 33.73, 28.72, 24.57, 24.32, 16.28, 8.38, 8.26

Compound 9 'Synthesis

Dissolve compound 8 ' (0.855 g, 0.79 mmol) in acetonitrile (8.5 mL) under nitrogen atmosphere, add tributylamine (1.17 g, 6.32 mmol), and connect the reflux condenser. After stirring for 48 hours at reflux, the solvent is removed by a rotary vacuum distillation apparatus. Diethyl ether (20 mL) was added and stirred for 15 minutes to precipitate a solid material. The solution was then decanted to remove only a solid compound. This process is repeated two more times to give a pale off-white solid compound. The obtained solid compound was added to AgBF ₄ (0.642 g, 3.30 mmol), is added slowly to the ethanol solution (40 mL) with stirring. After stirring for 24 hours in a light-blocked atmosphere, the resulting AgI was removed by filtration using celite. The solvent was removed under reduced pressure in vacuo and then dissolved in methylene chloride (6 mL) and filtered again using celite to remove suspended solids. Pure compound was obtained through silica gel column chromatography using methylene chloride-ethanol mixture (5: 1), from which the solvent was removed, as a developing solution (1.23 g, 90%).

¹ H NMR (CDCl ₃ ): δ. 13.55 (s, 1H, OH), 8.42 (s, 1H, CH = N), 7.12 (s, 1H, m -H), 7.08 (s, 1H, m -H), 3.38 (br, 1H, cyclohexyl- CH), 3.06 (br, 16H, NCH ₂ ), 2.20 (s, 3H, CH ₃ ), 1.88-1.84 (br, 2H, cyclohexyl-CH ₂ ), 1.68-1.26 (br, 36H), 0.87-0.86 ( br, 18H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ. 165.23, 157.79, 135.21, 131.17, 127.18, 125.76, 117.91, 72.05, 59.16, 58.63, 40.16, 38.10, 37.71, 26.45, 24.91, 23.90, 20.31, 19.80, 17.30, 16.01, 13.97, 13.80, 13.79

Example 3

Compound 10 'Synthesis

Compound 9 ' (100 mg, 0.06 mmol) and Co (OAc) ₂ (10.7 mg, 0.06 mmol) are added to the flask and dissolved by addition of ethanol (3 mL). After stirring for 3 hours at room temperature, the solvent is removed under reduced pressure. Diethyl ether (2 mL) was added and the mixture was stirred for 15 minutes, followed by precipitation of a solid material to remove the supernatant, and a red solid compound was obtained twice. The solvent was completely removed by distillation under vacuum, and methylene chloride (3 mL) was added to dissolve. Then, 2,4-dinitrophenol (11.1 mg, 0.06 mmol) was added thereto and stirred under an oxygen atmosphere for 3 hours. Sodium-2,4-dinitrophenolate (74.5 mg, 0.30 mmol) was added under an oxygen atmosphere, followed by stirring overnight. Filtration with Celite and vacuum removal of solvent gave compound (137 mg, 100%).

¹ H NMR (dmso-d _{6 ,} 38 ° C): δ. 8.65 (br, 2H, (NO ₂ ) ₂ C ₆ H ₃ O), δ. 7.88 (br, 3H, (NO ₂ ) ₂ C ₆ H ₃ O, CH = N), 7.31 (br, 2H, m -H), 6.39 (br, 2H, (NO ₂ ) ₂ C ₆ H ₃ O) , 3.38 (br, 1H, cyclohexyl-CH), 3.08 (br, 16H, NCH ₂ ), 2.64 (s, 3H, CH ₃ ), 2.06-1.85 (br, 2H, cyclohexyl-CH ₂ ), 1.50-1.15 ( br, 36H), 0.86 (br, 18H, CH ₃ ) ppm.

Example 4 Preparation of Carbon Dioxide / Propylene Oxide Copolymer

In a 50 mL bomb reactor, compound 10 ' prepared in Example 3 (6.85 mg, 0.0030 mmol, monomer / catalyst = 50,000) and propylene oxide (9.00 g, 155 mmol) were added to assemble the reactor. The reactor was immersed in an oil bath whose temperature was previously adjusted to 80 ° C. and stirred for about 15 minutes so that the reactor temperature was in equilibrium with the bath temperature. A carbon dioxide gas pressure of 20 bar was applied. The reaction proceeded after 30 minutes and the carbon dioxide pressure dropped. Carbon dioxide was continuously injected for 1 hour at a pressure of 20 bar. 10 g of the monomer was added to the obtained viscous solution to lower the viscosity of the solution, and then passed through a pad of silica gel (400 mg, manufactured by Merck, 0.040-0.063 mm particle size (230-400 mesh)) to obtain a colorless solution. Get The monomer was removed under reduced pressure in vacuo to yield 2.15 g of a white solid. This corresponds to an activity with a Turnover Number (TON) of 6100 and a Turnover Frequency (TOF) of 9200 h ⁻¹ . The molecular weight (Mn) measured using GPC of the obtained polymer is 89000 and the molecular weight distribution (Mw / Mn) is 1.21. ^The selectivity for polymer formation, analyzed by ¹ H NMR, is 96%.

Claims (23)

A compound of formula 1 [Formula 1]

[In Formula 1, A ¹ to A ⁴ are independently straight or branched chain (C 2 -C 20) alkylene or (C 3 -C 20) cycloalkylene; R ¹ is primary or secondary (C 1 -C 20) alkyl; R ² to R ⁴ are independently selected from (C 1 -C 20) alkyl or (C 6 -C 30) aryl; Q is a diradical which combines to connect two nitrogen atoms; Z ^- are each independently or at the same time, a halogen anion, BF ₄ ^- is selected _{^{from] -, ClO 4 -, NO}} 3 - or PF _6. The method of claim 1, In Formula 1, Q is (C6 ~ C30) arylene, (C1 ~ C20) alkylene, (C2 ~ C20) alkenylene, (C2 ~ C20) alkynylene, (C3 ~ C20) cycloalkylene or fused (C3-C20) cycloalkylene or the arylene, alkylene, alkenylene, alkynylene, cycloalkylene or fused cycloalkylene is a halogen atom, (C1-C7) alkyl, (C6-C30) aryl Or a substituent selected from nitro groups, or at least one hetero atom selected from oxygen, sulfur and nitrogen. The method of claim 1, In Formula 1, A ¹ to A ⁴ are propylene; R ¹ and R ² are methyl, R ³ and R ⁴ are butyl, Q is trans-1,2-cyclohexylene and Z ⁻ is independently an iodine anion or BF ₄ ⁻ . The method of claim 1, The compound is characterized in that the formula (2). [Formula 2]

[In Formula 1, m and n are independently an integer of 1 to 20; R ¹ is primary or secondary (C 1 -C 20) alkyl; R ² to R ⁴ are independently selected from (C 1 -C 20) alkyl or (C 6 -C 30) aryl; Q is a diradical which combines to connect two nitrogen atoms; Z ^- are each independently or at the same time, a halogen anion, BF ₄ ^- is selected _{^{from] -, ClO 4 -, NO}} 3 - or PF _6. The method of claim 4, wherein In Formula 2, Q is (C6 ~ C30) arylene, (C1 ~ C20) alkylene, (C2 ~ C20) alkenylene, (C2 ~ C20) alkynylene, (C3 ~ C20) cycloalkylene or fused (C3-C20) cycloalkylene or the arylene, alkylene, alkenylene, alkynylene, cycloalkylene or fused cycloalkylene is a halogen atom, (C1-C7) alkyl, (C6-C30) aryl Or a substituent selected from nitro groups, or at least one hetero atom selected from oxygen, sulfur and nitrogen. The method of claim 4, wherein In Formula 1, m and n are 2; R ¹ and R ² are methyl, R ³ and R ⁴ are butyl, Q is trans-1,2-cyclohexylene and Z ⁻ is independently an iodine anion or BF ₄ ⁻ . A cobalt complex compound represented by the following formula (3). (3)

[In Formula 3, A ⁵ to A ⁸ are independently straight or branched chain (C 2 -C 20) alkylene or (C 3 -C 20) cycloalkylene; R ⁵ is primary or secondary (C 1 -C 20) alkyl; R ⁶ to R ⁸ are independently selected from (C 1 -C 20) alkyl or (C 6 -C 30) aryl; Q is a diradical which combines to connect two nitrogen atoms; Z ¹ to Z ⁵ are independently a halogen anion; BF ₄ ^-; ClO ₄ ^-; NO ₃ ^-; PF ₆ ^-; HCO ₃ ^-; (C6-C30) aryloxy anion with or without halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C1-C20) carboxylic acid anion; (C1-C20) alkoxy anion; (C1-C20) alkylcarbonate anion; (C1-C20) alkyl sulfonate anion; (C1-C20) alkyl amido (amide) anion; Some of Z ¹ to Z ⁴ selected from (C 1 to C 20) alkylcarbamate anions and coordinated to cobalt may be decoordinated.] The method of claim 7, wherein In Formula 3, Q is (C6 ~ C30) arylene, (C1 ~ C20) alkylene, (C2 ~ C20) alkenylene, (C2 ~ C20) alkynylene, (C3 ~ C20) cycloalkylene or fused (C3-C20) cycloalkylene or the arylene, alkylene, alkenylene, alkynylene, cycloalkylene or fused cycloalkylene is a halogen atom, (C1-C7) alkyl, (C6-C30) aryl Or a cobalt complex, which may be further substituted with a substituent selected from a nitro group or comprises at least one hetero atom selected from oxygen, sulfur and nitrogen. The method of claim 7, wherein In Formula 3, A ⁵ to A ⁸ are independently straight or branched chain (C2 ~ C6) alkylene; R ⁵ is primary or secondary (C 1 -C 7) alkyl; R ⁶ to R ⁸ are independently (C 1 -C 7) alkyl; Q is ethylene, trans-1.2-cyclohexylene, or 1,2-phenylene; Z ¹ to Z ⁵ is 2,4-dinitro phenolate or BF ₄ ^{independently-cobalt} complex is selected from. The method of claim 9, In Formula 3, A ⁵ to A ⁸ are propylene; R ⁵ and R ⁶ are methyl, R ⁷ and R ⁸ are butyl, Q is trans-1,2-cyclohexylene, Z ¹ to Z ⁵ are independently 2,4-dinitrophenolate or BF ₄ ^cobalt complexes chosen from. The method of claim 7, wherein The cobalt complex is a cobalt complex represented by the following formula (4). [Formula 4]

[In Formula 4, p and q are independently an integer of 1 to 20; R ⁵ is a primary or secondary (C 1 -C 20) alkyl group; R ⁶ to R ⁸ are independently selected from (C1-C20) alkyl or (C6-C30) aryl groups; Q is a diradical which combines to connect two nitrogen atoms; Z ¹ to Z ⁵ are independently a halogen anion; BF ₄ ^-; ClO ₄ ^-; NO ₃ ^-; PF ₆ ^-; HCO ₃ ^-; (C6-C30) aryloxy anion with or without halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom; (C1-C20) carboxylic acid anion; (C1-C20) alkoxy anion; (C1-C20) alkylcarbonate anion; (C1-C20) alkyl sulfonate anion; (C1-C20) alkyl amido (amide) anion; Z ¹ to Z ⁴ selected from (C 1 -C 20) alkylcarbamate anions and coordinated to cobalt Some may be decoordinated.] The method of claim 11, In Formula 4, Q is (C6 ~ C30) arylene, (C1 ~ C20) alkylene, (C2 ~ C20) alkenylene, (C2 ~ C20) alkynylene, (C3 ~ C20) cycloalkylene or fused (C3-C20) cycloalkylene or the arylene, alkylene, alkenylene, alkynylene, cycloalkylene or fused cycloalkylene is a halogen atom, (C1-C7) alkyl, (C6-C30) aryl Or a cobalt complex, which may be further substituted with a substituent selected from a nitro group or comprises at least one hetero atom selected from oxygen, sulfur and nitrogen. The method of claim 11, In Formula 4, p and q are integers of 1 to 5; R ⁵ is primary or secondary (C 1 -C 7) alkyl; R ⁶ R ⁸ is independently (C 1 -C ⁷ ) alkyl; Q is ethylene, trans-1.2-cyclohexylene, or 1,2-phenylene; Z ¹ to Z ⁵ is 2,4-dinitro phenolate or BF ₄ ^{independently-cobalt} complex is selected from. The method of claim 13, In Formula 4, p and q are 2; R ⁵ and R ⁶ are methyl, R ⁷ and R ⁸ are butyl, Q is trans-1,2-cyclohexylene, Z ¹ to Z ⁵ are independently 2,4-dinitrophenolate or BF ₄ ^cobalt complexes chosen from. A phenol derivative represented by the following formula (5). [Chemical Formula 5]

[In Formula 5, A ⁹ and A ¹⁰ are independently straight or branched chain (C 2 -C 20) alkylene or (C 3 -C 20) cycloalkylene, and R ⁹ is primary or secondary (C 1 -C 20) Alkyl, R ¹⁰ is selected from (C1-C20) alkyl or (C6-C30) aryl, and X ¹ and X ² are independently selected from Cl or Br.] The method of claim 15, In Formula 5, A ⁹ and A ¹⁰ are alkylene of (C2 ~ C6), R ⁹ is primary or secondary (C1 ~ C7) alkyl, R ¹⁰ is primary or secondary (C1 ~ C7) Phenol derivatives which are alkyl. The method of claim 16, In Formula 5, A ⁹ and A ¹⁰ are propylene, R ⁹ and R ¹⁰ are methyl, and X ¹ and X ² are Cl. A method for producing a polycarbonate comprising copolymerizing an epoxide compound and carbon dioxide using the cobalt complex compound according to any one of claims 7 to 14. The method of claim 18, The epoxide compound is (C2 ~ C20) alkylene oxide unsubstituted or substituted with halogen or alkoxy; (C4-C20) cycloalkylene oxide unsubstituted or substituted with halogen or alkoxy; And (C8 ~ C20) styrene oxide substituted or unsubstituted with halogen, alkoxy, alkyl or aryl. The phenol derivative of formula (5) comprising the step of reacting a phenol compound of formula 6 and a tertiary alcohol compound of formula (7) under an acid catalyst. [Chemical Formula 5]

[Formula 6]

[Formula 7]

[In Formulas 5 to 7, A ⁹ and A ¹⁰ are independently a linear or branched (C 2 to C 20) alkylene group or (C 3 to C 20) cycloalkylene group, and R ¹¹ is primary or secondary (C 1 ~ C20) alkyl, R ¹² is selected from (C1-C20) alkyl or (C6 ~ C30) aryl, X ³ and X ^{4 are} independently selected from Cl or Br.] The method of claim 20, In Formulas 5 to 7, A ⁹ and A ¹⁰ are (C 2 -C 6) alkylene, R ¹¹ is primary or secondary (C 1 -C 7) alkyl, and R ¹² is (C 1 -C 7) alkyl. Derivative preparation method. The method of claim 21, In Chemical Formulas 5 to 7, A ⁹ and A ¹⁰ are propylene, and R ¹¹ and R ¹² are methyl. The method according to any one of claims 20 to 22, The acid catalyst is a phenol derivative manufacturing method selected from AlCl _{3 ,} inorganic acid or solid acid catalyst.