KR20140116833A - Catalytic system of nitrate anions for carbon dioxide/epoxide copolymerization - Google Patents

Abstract

The present invention relates to a salen type ligand including at least three quaternary ammonium salts of nitrate anion; a metal trivalent complex prepared from the ligand and a preparation method thereof; a method of preparing polycarbonate by copolymerizing an epoxide compound and carbon dioxide using the metal trivalent complex as a catalyst; and a separating and recovering method of the catalyst from the copolymer after copolymerization reaction. According to the present invention, the catalyst in the copolymerization of the epoxide compound and the carbon dioxide is obtained by a simple process, requires low price for preparing and recovering thereof, and has high activity when compared with a common catalyst.

Description

BACKGROUND ART Catalytic system of nitrate anions for carbon dioxide / epoxide copolymerization Catalytic system of nitrate anions for carbon dioxide /

The present invention relates to a salen-type ligand comprising three or more quaternary ammonium salts of nitrate anions; Metal trivalent complexes prepared from the ligands and a process for their preparation; A method of preparing a polycarbonate by copolymerizing an epoxide compound and carbon dioxide using this as a catalyst; And a process for separating and recovering the catalyst from the copolymer after the copolymerization reaction.

The aliphatic polycarbonate is a biodegradable polymer which is useful as, for example, a packaging material or a coating material. The method of producing polycarbonate from an epoxide compound and carbon dioxide is environmentally-friendly in that it does not use poisonous compound phosgene and that carbon dioxide can be obtained at low cost.

Since the 1960s, many researchers have developed various types of catalysts to produce polycarbonates from epoxide compounds and carbon dioxide. Recent research has salen [Salen containing the quaternary ammonium salt _{to: ([H 2 Salen = N} , N '-bis (3,5-dialkylsalicylidene) -1,2-ethylenediamine] - The high activity is synthesized from a ligand of the type , A high selectivity catalyst has been disclosed [This division, Korean Patent Registration 10-0853358 (Registered Date: Aug. 13, 2008); Split, Sujith S, Noh Eun Kyung, Min Jae Kee, Korean Patent Application 10-2008-0015454 Sujith S, Sang-Wook Kim, and Eun Kyung Noh, Eun Kyung Noh, and Sujith S, 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 can exhibit high activity and high selectivity, can produce a copolymer having a high molecular weight, can be polymerized at a high temperature, and can be applied to commercial processes. Also, since the quaternary ammonium salt is contained in the ligand, the catalyst can be easily separated from the copolymer after the carbon dioxide / epoxide copolymerization reaction and reused.

Further, the present inventors have carefully analyzed the structure of a catalyst showing particularly high activity and high selectivity in comparison with the catalyst group of the above patent, and found that the structure of the catalyst does not coordinate the nitrogen atom of the Salen- (See Structure 1 below.) (See Structure 1, Sung Jae Na, Sujith S, Anish Cyriac, Bo Eun Kim, Jina Yoo, Youn K. Kang, Su Jung Han, Chongmok Lee, and Bun Yeoul Lee * "Elucidation of the Structure of A Highly Active Catalytic System for CO 2 / Epoxide Copolymerization: A Salen-Cobaltate Complex of An Unusual Binding Mode" Inorg. Chem. 2009 , 48 , 10455-10465).

Also, a method for easily synthesizing the ligand of the compound has been developed (Min, J .; Seong, JE; Na, SJ; Cyriac, A .; Lee, BY Bull. Korean Chem. Soc. 2009 , 30 , 745-748). However, considering the commercial process input of the highly active catalyst of Structure 1 above, it has the following problems:

1) 2,4-dinitrophenolate or 2,4-dinitrophenol, which is included in the catalyst of Structure 1 above, is known as an explosive substance. (KR Desai, BG Naik, Production of Organic Intermediates (Phamaceutical and Dyestuff) , Sarup & Sons, New Delhi, 2005; p 5). The catalyst of Structure 1 above must be prepared and stored under dry conditions. It is manufactured in large quantities and is unsuitable for continuous use.

2) When carbon dioxide / epoxide copolymerization is carried out using the catalyst of Structure 1, the polymer chain is grown from 2,4-dinitrophenolate or 2,4-dinitrophenol, which is included in the catalyst of Structure 1 above. That is, 2,4-dinitrophenol groups are attached to most polymer chain terminals. Namely, in the catalyst recovery step, 2,4-dinitrophenolate and 2,4-dinitrophenol are not recovered. Attaching the 2,4-dinitrophenol group to all the polymer chain terminals increases the unit cost of the resin. In addition, the 2,4-dinitrophenolate anion is fairly yellowish, which can cause the resin to remain pale yellow even after removal of the catalyst.

3) The production cost of the catalyst of Structure 1 is high. The synthesis method is shown below ( Bull. Korean Chem. Soc. 2009 , 30 , 745-748). Under this method, it is burdensome to mass-produce in the following points.

i) The AgBF ₄ used in the first step is a very expensive compound, which is the main cause of the high catalyst production cost and is not easy to manufacture or purchase in large quantities.

ii) The second step is to proceed the reaction in an oxygen-free atmosphere. In other words, oxygen must be thoroughly removed from the ethanol used. It is not easy to thoroughly remove oxygen from ethanol.

iii) The sodium 2,4-dinitrophenolate used in the third step should be free of moisture, and NaH and anhydrous THF solvent should be used to produce moisture-free sodium 2,4-dinitrophenolate. However, NaH is expensive and is highly inflammable, which is a great burden to handle in large quantities. In addition, removing moisture from the THF solvent is also a great burden in mass production.

4) NaBF ₄ is used for catalyst recovery in Structure 1 above, but NaBF ₄ is expensive and not economical.

In addition, a similar type of compound having a nitrate anion has been disclosed in the Chinese patent. However, when R ⁵ and R ⁶ contain a quaternary ammonium salt and the total number is 2 and R ¹ , R ² , R ⁵ , and R ⁶ ammonium Only compounds with four salts are given in a limited manner and are outside the range of the complexes provided by the present invention (CN 100494248C (2009.06.03)).

In studying to overcome the above problems, the present inventors have found that by introducing nitrate and acetate anion instead of 2,4-dinitrophenolate, the problems of 1) and 2) . In addition, AgNO ₃ or Ag (OAc) other than AgBF ₄ is used in the synthesis of a catalyst in which nitrate and acetate anion are introduced, which makes it possible to manufacture and purchase in large quantities and to use oxygen-free ethanol No sodium 2,4-dinitrophenolate was used, and NaH and anhydrous THF were not needed, thereby solving the problem 3) of the catalyst of Structure 1 above was solved. In addition, by using nitric acid or nitrate, which is relatively low in price in place of NaBF _4, which is conventionally used in the catalyst recovery step, the problem of 4) in the catalyst of Structure 1 can be solved.

Therefore, a first object of the present invention is to provide a Salen-type ligand comprising at least three quaternary ammonium salts of nitrate anions, metal trivalent complexes prepared from the ligands and a process for their preparation.

A second object of the present invention is to provide a method for producing a polycarbonate by copolymerizing an epoxide compound and carbon dioxide using the complex as a catalyst.

A third object of the present invention is to provide a method for separating and recovering a catalyst from a mixed solution of a copolymer and a catalyst obtained by preparing a copolymer using the complex as a catalyst.

In order to achieve the object of the present invention, there is provided a compound having a structure represented by the following formula (1).

[Chemical Formula 1]

[In the above formula (1)

M is a cobalt trivalent or chromium trivalent;

A is an oxygen or sulfur atom;

Q is a diradical linking two nitrogen atoms;

R ¹ and R ² is independently a primary (C1-C20) alkyl and the other;

R ³ - R ¹⁰ is independently from each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl;

The R &^lt; ^{1 &} R ¹⁰ Two of which may be connected to each other to form a ring;

The R < ^{3 &} At least three of R < ¹⁰ > are a proton residue selected from the group consisting of the following formula a, b and c;

Z is nitrogen or phosphorus;

R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ independently of one another are (C 1 -C 20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ¹¹ , R ¹² and R ¹³ or two of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ may be connected to each other to form a ring;

R ³¹ , R ³² and R ³³ independently of one another are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ³¹ , R ³² and R ³³ may be connected to each other to form a ring;

X 'is oxygen, sulfur or N-R wherein R is (C1-C20) alkyl;

a is R < ³ > The number of protons included in R < ¹⁰ > + 1;

b is an integer of 1 or more;

The nitrate or acetate anion may also be coordinated to M.

The present invention provides a compound which necessarily comprises a nitrate anion and consists of some acetate anion. The nitrate anion is not claimed in the Korean Registered Patent Registration No. 10-0853358 published by the inventor of the present invention and the anion is aryloxy having 1 to 20 carbon atoms substituted or unsubstituted with a halogen atom, And is limited to a carboxylic anion having 1 to 20 carbon atoms which is substituted or unsubstituted with halogen, and thus is different from the present invention. The present invention is not explosive by introducing nitrate and acetate anion in place of 2,4-dinitrophenolate, and has the advantage of having a low catalyst cost in mass production due to the addition of a nitro group or an acetate group to the polymer chain terminal.

The catalyst of Structure 1 of the background art is highly active since it has an octahedrally ordered structure in which cobalt is negatively charged and the anion of the quaternary ammonium salt is coordinated without nitrogen coordination ( Inorg. Chem. 2009 , 48 , 10455 -10465).

The nitrate anion, which is a feature of the present invention, is weak in dewaxing ability and can not be strongly coordinated to cobalt, so that it is difficult to form a structure in which a nitrogen such as a catalyst of Structure 1 is not coordinated and anions of quaternary ammonium salts are coordinated. However, when the polymerization reaction is initiated, the nitrate anion reacts with the monomer to become a carbonate anion or an alkoxy anion. The carbonate anion or the alkoxy anion is strong enough to form a structure in which anion of the quaternary ammonium salt is coordinated with no nitrogen such as the catalyst of Structure 1 above. In order to have the same structure as that of the catalyst of Structure 1 showing high activity after initiation of the polymerization reaction, the number of onium salts should be 3 or more and primary alkyl of R ¹ and R ² should not be large. When R ¹ and R ² are tertiary alkyl or secondary alkyl, the same polymerization structure as the catalyst of Structure 1 is not formed and polymerization activity is low. Also, when the number of onium salts is 2 or less, the same polymerization structure as that of the catalyst of Structure 1 is not formed and the polymerization activity is low ( Inorg. Chem. 2009 , 48 , 10455-10465).

Preferably, in the above formula (1), M is cobalt trivalent; A is oxygen; Q is (C6 to C30) arylene, (C1 to C20) alkylene, (C2 to C20) alkenylene, (C2 to C20) alkynylene or (C3 to C20) cycloalkylene, more preferably Q is Trans-1,2-cyclohexylene, phenylene or ethylene; R ¹ and R ² is independently methyl or ethyl with one another; R ³ - R ¹⁰ is independently from each other hydrogen or - [YR ⁴¹ _3-m {(CR ⁴² R ⁴³ ) _n N ⁺ R ⁴⁴ R ⁴⁵ R ⁴⁶ } _m ]; Y is C or Si; R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ independently from each other are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of Group 14 metal substituted with hydrocarbyl, R ^44, Two of R ⁴⁵ and R ⁴⁶ may be connected to each other to form a ring; m is an integer from 1 to 3, and n is an integer from 1 to 20; Provided that when m is 1, R < ³ > At least three or more of the R ¹⁰ is _{^{- [YR 41 3-m {}} (CR 42 R 43) n N + R 44 R 45 R 46} a] and, when m is 2 R ³ to At least two or more of R ¹⁰ is _{^{- [YR 41 3-m {}} (CR 42 R 43) n N + R 44 R 45 R 46} m] , and when m is 3 to R ^{3 At} least one of R ¹⁰ is - [YR ⁴¹ _3-m {(CR ⁴² R ⁴³ ) _n N ⁺ R ⁴⁴ R ⁴⁵ R ⁴⁶ } _m ].

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

(2)

[In the formula (2)

R ⁵¹ and R ⁵² independently of one another are methyl or ethyl;

R ⁵³ and R ⁵⁴ independently of one another are hydrogen or methyl;

Q is trans-1, 2-cyclohexylene, phenylene or ethylene;

n is an integer from 1 to 20;

It can be coordinated to cobalt to nitrate anion and acetate anion.]

More preferably, R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ in the general formula (2) are methyl, n is 3, and Q is trans-1, 2-cyclohexylene.

In another aspect of the present invention, there is provided a process for producing a polycarbonate comprising copolymerizing an epoxide compound and carbon dioxide using the complex of Formula 1 as a catalyst.

The epoxide compound is a (C2-C20) alkoxy substituted or unsubstituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6- Alkylene oxides; (C4-C20) cycloalkylene oxides unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) aralkyloxy; And (C8-C20) aralkyloxy which is unsubstituted or substituted by halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6- -C20) styrene oxide. Examples of the aryloxy include phenoxy, biphenyloxy, naphthyloxy, and the like. The alkyloxy, aryloxy, aralkyloxy and alkyl may have a substituent selected from a halogen atom 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, Epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, t-butyl glycidyl ether, 1,2-epoxide-7-octene, epifluorohydrin, epichlorohydrin, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxide norbornene, limonene oxide, Diallylene, 2,3-epoxide propylbenzene, styrene oxide, phenylpropylene oxide, stilbeneox Epoxidized propyl ether, epoxidized propyl ether, epoxidized propyl ether, butyl acrylate, ethyl acrylate, ethyl acrylate, ethyl acrylate, ethyl acrylate, Propyl methoxyphenyl ether biphenyl glycidyl ether, and glycidyl naphthyl ether.

Examples of the solvent include aliphatic hydrocarbons such as pentane, octane, decane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, aromatic hydrocarbons such as chloromethane, methylene chloride , Chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, ethyl chloride, trichloroethane, 1- chloropropane, 2- chloropropane, 1- chlorobutane, 2- -Chloro-2-methylpropane, halogenated hydrocarbons such as chlorobenzene and bromobenzene, or a combination of two or more of them. More preferably, bulk polymerization can be carried out using the monomer itself as a solvent.

The molar ratio of the epoxide compound to the catalyst, that is, the epoxide compound: catalyst molar ratio is 1,000 to 1,000,000, preferably 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 per hour, may be 500 turnsover / hr or more. In the copolymerization step, the pressure of the carbon dioxide can be from normal pressure to 100 atm, preferably at 5 atm and 30 atm. In the copolymerization step, the polymerization temperature may range from 20 占 폚 to 120 占 폚, preferably from 50 占 폚 to 90 占 폚.

Polycarbonate can be polymerized by a batch polymerization method, a semi-batch polymerization method or a continuous polymerization method. In the case of using a batch or semi-batch polymerization method, the reaction time may be 1 to 24 hours, preferably 1.5 to 4 hours. The average residence time of the catalyst in the case of using the continuous polymerization method is also preferably 1.5 to 4 hours.

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

The prepared polycarbonate polymer is composed of at least 80% carbonate bond, often at least 95% carbonate bond. The polycarbonate produced according to the present invention is a polymer which is easy to decompose and has no residue or soot upon combustion, and is useful as, for example, a packaging material, an insulating material, or a coating material.

(C 1 -C 20) alkyloxy, (C 6 -C 20) aryloxy or (C 6 -C 20) alkoxy, by using a complex of the formula (3) (C2-C20) alkylene oxide substituted or unsubstituted with aryl (C1-C20) aralkyloxy; (C4-C20) cycloalkylene oxides unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) aralkyloxy; And (C8-C20) aralkyloxy which is unsubstituted or substituted by halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6- -C20) styrene oxide, and carbon dioxide to prepare a polycarbonate; And a solution in which the prepared copolymer and the catalyst are dissolved is contacted with a solid inorganic material, a polymer material or a mixture thereof, which is not soluble in the solution, to form a complex of the solid inorganic material or polymer and the catalyst, And separating the catalyst from the catalyst. The present invention also provides a method for producing the polycarbonate.

(3)

[In the above formula,

M is a cobalt trivalent or chromium trivalent;

A is oxygen or sulfur;

Q is a diradical linking two nitrogen atoms;

R ¹ - R ¹⁰ is independently from each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl;

The R &^lt; ^{1 &} R ¹⁰ Two of which may be connected to each other to form a ring;

The R < ^{3 &} At least one of R < ¹⁰ > is a proton residue selected from the group consisting of the following structural formulas a, b and c;

Z is nitrogen or phosphorus;

R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ independently of one another are (C 1 -C 20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ¹¹ , R ¹² and R ¹³ or two of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ may be connected to each other to form a ring;

R ³¹ , R ³² and R ³³ independently of one another are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ³¹ , R ³² and R ³³ may be connected to each other to form a ring;

X 'is oxygen, sulfur or N-R wherein R is (C1-C20) alkyl;

a is R < ³ > The number of protons included in R < ¹⁰ > + 1;

b is an integer of 1 or more, b + c is the same as the value of a;

The nitrate or acetate anion may also be coordinated to M.

The mechanism of the catalyst removal method provided by this patent is the same as the method disclosed by the present inventor (Korean Patent Application No. 10-2008-0015454; Angew. Chem. Int. Ed. , 2008 , 47, 7306-7309. 2008.09.08)). However, the disclosed patent does not include a compound in which anion is nitrate. Carbon dioxide / epoxide copolymerization using a similar type of compound having a nitrate anion is disclosed in the Chinese patent, but there is no mention about the catalyst removal method (CN 100494248C (2009.06.03)). the copolymer and of the copolymer as well as how to remove the catalyst, R ¹ and R ² is necessarily not a primary alkyl, onium salts Conger number of two or less is then more in the polymerization activity can be somewhat poor wide range, A polymerization obtained by using the compound of Formula 3 and a method of separating the polymer from the catalyst.

The solid inorganic material may be silica or alumina that is not surface-modified or surface-modified, and the polymer material may be a polymer material having a functional group capable of causing a deprotonation reaction by an alkoxy anion. The alkoxy anion may cause a deprotonation reaction The functional group that can occur is a sulfonic acid group, a carboxylic acid group, a phenol group or an alcohol group.

Specific examples of the solid inorganic material containing silicon or aluminum as a main component including a brent acid acid point capable of providing a proton to an alkoxy anion or carbonate anion include silica, alumina, aluminosilicate (zeolite), aluminophosphate, Titanium silicate, clay, or the like, and it is more preferable to use silica or alumina that is not surface-modified or surface-modified.

It is preferable that the polymer material is crosslinked with a number average molecular weight of 500 to 10,000,000, but it is possible that it is not dissolved in a solution containing a copolymer and a catalyst even if it is not crosslinked. More specific examples of the "polymer substance having a functional group capable of causing a deprotonation reaction by an alkoxy anion" include a copolymer containing a unit such as the following structural formulas A to E in a polymer chain, or a homopolymer composed of such a unit. . The polymer substance serving as such a support may be not crosslinked unless dissolved in the above-mentioned solution, but it is preferable that the polymer substance is crosslinked appropriately in order to lower the solubility.

(C6-C20) aryloxy or (C6-C20) aryl (C1-C20) alkyl (C1-C60) alkyl (C2-C20) alkylene oxide substituted or unsubstituted with an aralkyloxy group; (C4-C20) cycloalkylene oxides unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) aralkyloxy; And (C8-C20) aralkyloxy which is unsubstituted or substituted by halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6- -C20) styrene oxide, and carbon dioxide to prepare a polycarbonate; A solution in which the prepared copolymer and the catalyst are dissolved is contacted with a solid inorganic material, a polymer substance or a mixture thereof, which is not soluble in the solution, to form a composite of the solid inorganic material or the polymer substance and the catalyst, Separating the catalyst; And treating the composite of the solid inorganic material or the polymer substance with the catalyst with nitric acid or nitrate in a medium which can not dissolve the complex of the solid inorganic material or polymer substance with the catalyst so that the precursor of the catalyst or catalyst is separated from the medium And separating and recovering the catalyst and the catalyst precursor by dissolving the catalyst precursor and the catalyst precursor in the solution, and separating and recovering the catalyst and the catalyst precursor from the solution in which the catalyst is dissolved. Most preferred as the medium is ethanol or methanol.

In the previously disclosed catalyst recovery method, NaBF _4, which is a non-reactive salt, was used (Korean Patent Application 10-2008-0015454; Angew. Chem. Int. Ed. , 2008 , 47, 7306-7309 In the invention, nitric acid or nitrate, whose price is relatively low, was used.

In another embodiment of the present invention, a compound of formula 4 is reacted with a mixture of a halogen anion equivalent of silver nitrate (AgNO ₃ ) or silver nitrate (AgNO ₃ ) and silver acetate (AgOC (O) CH ₃ ) 5 < / RTI > And reacting cobalt (II) acetate or chromium (II) acetate with a compound of formula (5) in the presence of oxygen to produce a complex of formula (1).

[Chemical Formula 1]

[Chemical Formula 4]

[Chemical Formula 5]

[In the above formulas (1), (4) and (5)

M is a cobalt trivalent or chromium trivalent;

A is an oxygen or sulfur atom;

Q is a diradical linking two nitrogen atoms;

X ^- is a halogen anion;

R ¹ and R ² is independently a primary (C1-C20) alkyl and the other;

R ³ - R ¹⁰ is independently from each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl;

The R &^lt; ^{1 &} R ¹⁰ Two of which may be connected to each other to form a ring;

The R < ^{3 &} At least three of R < ¹⁰ > are a proton radical selected from the group consisting of the following formula a, b and c;

Z is nitrogen or phosphorus;

R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ independently of one another are (C 1 -C 20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ¹¹ , R ¹² and R ¹³ or two of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ may be connected to each other to form a ring;

R ³¹ , R ³² and R ³³ independently of one another are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ³¹ , R ³² and R ³³ may be connected to each other to form a ring;

X 'is oxygen, sulfur or N-R wherein R is (C1-C20) alkyl;

a is R < ³ > The number of protons included in R < ¹⁰ > + 1;

b is an integer of 1 or more;

The nitrate or acetate anion may also be coordinated to M.

AgNO ₃ or Ag (OAc) used in the catalyst synthesis of the present invention is significantly lower in price than AgBF ₄ and can be prepared and purchased in large quantities. There is no step of using oxygen-free ethanol, Nitrophenolate is not used and NaH and anhydrous THF are unnecessary.

Preferably, in the above Chemical Formulas (1), (4) and (5), M is a cobalt trivalent; A is oxygen; Q is trans-1, 2-cyclohexylene, phenylene or ethylene; R ¹ and R ² is independently methyl or ethyl with one another; R ³ - R ¹⁰ is independently from each other hydrogen or - [YR ⁴¹ _3-m {(CR ⁴² R ⁴³ ) _n N ⁺ R ⁴⁴ R ⁴⁵ R ⁴⁶ } _m ]; Y is C or Si; R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ independently from each other are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of Group 14 metal substituted with hydrocarbyl, R ^44, Two of R ⁴⁵ and R ⁴⁶ may be connected to each other to form a ring; m is an integer from 1 to 3, and n is an integer from 1 to 20; Provided that when m is 1, R < ³ > At least three or more of the R ¹⁰ is _{^{- [YR 41 3-m {}} (CR 42 R 43) n N + R 44 R 45 R 46} a] and, when m is 2 R ³ to At least two or more of R ¹⁰ is _{^{- [YR 41 3-m {}} (CR 42 R 43) n N + R 44 R 45 R 46} m] , and when m is 3 to R ^{3 At} least one of R ¹⁰ is - [YR ⁴¹ _3-m {(CR ⁴² R ⁴³ ) _n N ⁺ R ⁴⁴ R ⁴⁵ R ⁴⁶ } _m ].

More preferably, reacting a compound of formula (VI) with 4 equivalents of silver nitrate (AgNO ₃ ) to prepare a compound of formula (7); And reacting cobalt (II) acetate with a compound of formula (7) in the presence of oxygen to produce a compound of formula (2).

(2)

[Chemical Formula 6]

(7)

[In the above formulas (2), (6) and (7)

X ^- is a halogen anion,

R ⁵¹ and R ⁵² independently of one another are methyl or ethyl;

R ⁵³ and R ⁵⁴ independently of one another are hydrogen or methyl;

Q is trans-1, 2-cyclohexylene, phenylene or ethylene;

n is an integer from 1 to 20;

It can be coordinated to cobalt to nitrate anion and acetate anion.]

In the above Chemical Formulas 2, 6 and 7, R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ are methyl, n is 3, and Q is more preferably trans-1,2-cyclohexylene.

The formula (6) and the synthesis of the compound of formula (VII) are known in the known papers and patents by the present inventor (Republic of Korea Patent Registration Registration 10-0853358 (date:.... 2008.08.13); Angew Chem Int Ed, 2008 , 47, 7306-7309; Bull. Korean Chem. Soc., 2009 , 30 , 745-748).

Conventional synthesis methods use explosive 2,4-dinitrophenolate or 2,4-dinitrophenol and use a catalyst containing the same to produce 2,4-dinitrophenol in a polymer chain terminal upon carbon dioxide / Since the dinitrophenol group is attached, 2,4-dinitrophenolate and 2,4-dinitrophenol are not recovered in the catalyst recovery step. As a result, the unit cost of the resin increases and the color of the resin may change. In addition, since expensive AgBF ₄ is used in the production of the catalyst, and a solvent such as anhydrous ethanol and anhydrous THF is used, NaH having a complicated catalyst preparation and high pyrophoricity is used. In addition, NaBF ₄ is expensive when recovering the catalyst, which is not economical.

The method of preparing the complex of the novel structure according to the present invention is as follows: 1) it is not burdensome to produce a large amount of catalyst by using nitrate anion and acetate anion instead of explosive 2,4-dinitrophenolate; 2) 3) The cost of catalyst production is low by using AgNO _3, which does not use expensive AgBF ₄ , but is low in unit cost and can be purchased and purchased in large quantities, because the catalyst or acetate group is attached. In addition, since a solvent such as ethanol-free anhydrous THF and the like is not used, the production of the catalyst is simple. Do not use NaH with high ignitability. Furthermore, it is economical to use nitric acid or nitrate instead of expensive NaBF ₄ for catalyst recovery.

Also, the catalyst used after the carbon dioxide / epoxide copolymerization reaction is separated and recovered by using the complex according to the present invention as a catalyst, thereby lowering the cost of the catalyst, thereby realizing economical efficiency in the production of the copolymer. By removing the catalyst, it becomes possible to produce a copolymer having high purity, thereby widening the range of use of the copolymer and improving the durability and processability of the copolymer.

The following Examples and Comparative Examples illustrate the effects of the present invention in detail. However, the following examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention.

[Example 1] Synthesis of catalyst (Compound C )

A simple and economical catalyst synthesis method of the present invention is shown below. Compound A was synthesized by a known method ( Bull. Korean Chem. Soc. 2009 , 30 , 745-748).

compound B Synthesis of

Compound A (100 mg, 0.054 mmol) and AgNO ₃ (37.3 mg, 0.219 mmol) were dissolved in ethanol (3 mL) and stirred overnight. The AgI was removed by filtration using celite. The solvent was removed in vacuo to give Compound B in the form of a yellow solid powder (0.80 g, 94%).

_{^{1 H NMR (CDCl 3):}} δ13.51 (s, 2H, OH), 8.48 (s, 2H, CH = N), 7.15 (s, 4H, m -H), 3.44 (br, 2H, cyclohexyl-CH ), 3.19 (br, 32H, NCH 2), 2.24 (s, 6H, CH 3), 1.57-1.52 (br, 4H, cyclohexyl-CH 2), 1.43-1.26 (br, 74H), 0.90-070. _{(br, 36H, CH 3)} ppm.

compound C Synthesis of

Compound B (95 mg, 0.061 mmol) and Co (OAc) ₂ (10.7 mg, 0.061 mmol) were placed in a flask and 3 mL of methylene chloride was added to dissolve. After stirring at room temperature for 3 hours under an oxygen atmosphere, the solvent was removed under reduced pressure to obtain Compound C in the form of a brown solid powder (85 mg, 83%).

_{^{1 H NMR (DMSO-d 6}} , 38 ℃℃): major signal set, δ 7.83 (s, 2H, CH = N) 7.27 (br s, 2H, mH), 7.22, 7.19 (brs, 2H, m -H ), 3.88 (br, 1H, cyclohexyl-CH), 3.55 (br, 1H, cyclohexyl-CH), 3.30-2.90 (br, 32H, NCH 2), 2.58 (s, 3H, CH 3), 2.55 (s, _{3H, CH 3), 2.10-1.80 (} br, 4H, cyclohexyl-CH 2), 1.70-1.15 (br m, 74H), 1.0-0.80 (br, 36H, CH 3) ppm; (S, 2H, m- H), 3.60 (br, 2H, cyclohexyl-CH), 3.30-2.90 (s, 2H, _{br, 32H, NCH 2),} 2.66 (s, 6H, CH 3), 2.10-1.80 (br, 4H, cyclohexyl-CH 2), 1.70-1.15 (br m, 74H), 1.0-0.80 (br, 36H, CH ₃₎ ppm.

^{_{1 H NMR (CD 2 Cl 2}} ): δ 7.65 (br, 2H, CH = N) 7.34 (br, 2H, mH), 7.16 (br, 2H, m -H), 3.40-2.00 (br, 32H, NCH _{2), 2.93 (br s,} 6H, CH 3), 2.10-1.80 (br m, 4H, cyclohexyl-CH 2), 1.70-1.15 (br m, 74H), 1.1-0.80 (br, 36H, CH 3) ppm.

Two sets of signals were observed at a ratio of 6: 4 in the ¹ H NMR spectrum obtained by dissolving in DMSO-d ₆ . The major signal set shows that the two phenoxy ligands of the Salen-units are different, and the minor signal set shows that the two phenoxy ligands are the same. This can be interpreted as the equilibrium state of Compound C as described below in DMSO solvent. It has been found that when a substituent having a small steric hindrance such as methyl is present at the o-position of the two phenoxy ligands of the Salen-unit, the structure of the imine nitrogen is not coordinated in a polar solvent like DMSO ( Inorg. Chem. 2009 , 48 , 10455-10465). In the non-polar solvent methylene chloride an overall broad set of signals was observed. Considering the fact that NO ₃ ^- anion is weak in ionization power, it is expected that the nitrogen atom is coordinated with imine and the nitrate anion and acetate anion are exchanged with each other, .

[Example 2] Carbon dioxide / propylene oxide copolymerization

Compound C (3.0 mg, monomer / catalyst = 100,000) and propylene oxide (10.0 g, 172 mmol) prepared in Example 1 were placed in a 50 mL bomb reactor and the reactor was assembled. After the carbon dioxide gas pressure of 15 bar was applied to the reactor, the reactor was immersed in an oil bath whose temperature was adjusted to 73 ° C and stirring was started. After 35 minutes, the internal temperature of the reactor reached 70 DEG C and from this point the reactor pressure was observed to decrease. The polymerization reaction was carried out for 1 hour from the start of the reaction when the internal temperature of the reactor reached 70 ° C. The reactor was immersed in a cold bath, cooled, and the reaction was terminated by removing the carbon dioxide gas. A pale yellow mucilage solution was obtained.

[Example 3] Catalyst separation

10 g of propylene oxide was further added to the mucolytic solution prepared in Example 2 to lower the viscosity of the solution. The solution was passed through a silica gel (400 mg, manufactured by Merck, 0.040-0.063 mm particle diameter (230-400 mesh) The monomer was removed by vacuum depressurization to give 2.4 g of a colorless solid which corresponds to an activity with a TON (Turnover Number) of 15000 and a TOF (Turnover Frequency) of 15000 h ^-1 . The molecular weight (Mn) measured by GPC was 217000 and the molecular weight distribution (Mw / Mn) was 1.34. The selectivity for polymer formation analyzed by ¹ H NMR was over 99%.

[Example 4] Catalyst precursor recovery

A reddish-brown cobalt compound was extracted using a methanol solution saturated with NaNO ₃ in the silica column on which the catalyst obtained in Example 3 was suspended as a developing solution. All of the yellow compounds could be extracted, and the color of the silica column became white unique to silica. Methanol was removed from the extract by vacuum distillation. Dichloroethane (3 mL) was added and filtered to remove excess NaNO ₃ . To the filtrate was added 1 mL of a 2 N HNO ₃ aqueous solution and the mixture was stirred overnight at 85 ° C. The aqueous layer was removed and the organic layer was washed with 1 mL of water. The organic layer was dried over anhydrous MgSO ₄ and the solvent was removed under reduced pressure. The following aldehyde compound was obtained by silica gel column chromatography using a mixed solvent of ethanol and methylene chloride 10: 1. The recovery rate was 90%. The catalyst can be easily prepared from the aldehyde compound.

Claims (1)

(C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) aralkyloxy, using a complex of the formula (C2-C20) alkylene oxide; (C4-C20) cycloalkylene oxides unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) aralkyloxy; And (C8-C20) aralkyloxy which is unsubstituted or substituted by halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6- -C20) styrene oxide, and a polycarbonate prepared by copolymerizing carbon dioxide.
[Chemical Formula 1]

[In the above formula (1)
M is a cobalt trivalent or chromium trivalent;
A is an oxygen or sulfur atom;
Q is a diradical linking two nitrogen atoms;
R ¹ and R ² is independently a primary (C1-C20) alkyl and the other;
R ³ - R ¹⁰ is independently from each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl;
The R &^lt; ^{1 &} R ¹⁰ Two of which may be connected to each other to form a ring;
The R < ^{3 &} At least three of R < ¹⁰ > are a proton residue selected from the group consisting of the following formula a, b and c;

Z is nitrogen or phosphorus;
R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ independently of one another are (C 1 -C 20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ¹¹ , R ¹² and R ¹³ or two of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ may be connected to each other to form a ring;
R ³¹ , R ³² and R ³³ independently of one another are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ³¹ , R ³² and R ³³ may be connected to each other to form a ring;
X 'is oxygen, sulfur or NR (where R is (C1-C20) alkyl);
a is R < ³ > The number of protons included in R < ¹⁰ > + 1;
b is an integer of 1 or more;
The nitrate or acetate anion may also be coordinated to M.