JP2011213982A - Method for producing polycarbonate using metal complex, the metal complex, and catalyst system including the metal complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing polycarbonate using a metal complex, the metal complex useful for producing the polycarbonate from an epoxide compound and carbon dioxide, and a catalyst system including the metal complex.SOLUTION: In the method for producing the polycarbonate, copolymerization of the epoxide compound and carbon dioxide is carried out in the presence of the metal complex comprising a quadrivalent metal and divalent/trivalent tetradentate ligands, which are subjected to tetradentate coordination with the quadrivalent metal via one or more kinds of hetero atoms selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus. The catalyst system including the metal complex and a cocatalyst, and a novel metal complex are also provided.

Description

  The present invention relates to a method for producing polycarbonate, comprising copolymerizing epoxide and carbon dioxide in the presence of a metal complex. The invention also relates to metal complexes and catalyst systems comprising metal complexes that are useful for producing polycarbonates from epoxides and carbon dioxide.

  Polycarbonate obtained by copolymerization of an epoxide compound and carbon dioxide is interesting in that carbon dioxide is used as a raw material for synthetic resins. In addition, since aliphatic polycarbonate has transparency and is completely decomposed when heated to a predetermined temperature or higher, it can be used for applications such as general molded products, films, fibers, and optical fibers such as optical fibers and optical disks. It can also be used as a material or a thermally decomposable material such as a ceramic binder or lost foam casting. Furthermore, since aliphatic polycarbonate can be decomposed in vivo, it can be applied as a medical material such as a sustained-release drug capsule, an additive of a biodegradable resin, or a main component of a biodegradable resin.

  As a catalyst used for copolymerization of epoxide and carbon dioxide, for example, Patent Document 1 (US Pat. No. 3,585,168) discloses a reaction product of diethyl zinc and water as described in Non-Patent Document 1 (J. Controlled Release, 1997, 49, 263) describe a reaction product of diethyl zinc and ethylene glycol, respectively.

  As a non-zinc-based catalyst, for example, Non-Patent Document 2 (H. Koinuma and H. Hirai, Makromol. Chem., 178, 1283-1294 (1977)) describes a triethylaluminum-water catalyst as described in Non-Patent Document 3 ( W. Kuran, T. Listos, M. Abramczyk, and A. Dawidek, J. Macromol. Sci., Pure Appl. Chem., A35, 427-437 (1998)) from diethylaluminum chloride and calixarene derivatives. Non-Patent Document 4 (DJ Darensbourg, EL Maynard, MW Holtcamp, KK Klausmeyer, and JH Reibenspies, Inorg. Chem., 35, 2682-2684 (1996)) prepared trispyrazolyl borate. Each aluminum complex in the ligand is described.

  US Patent Application Publication No. 2006/0089252 describes a catalyst system in which a cobalt-based catalyst having a specific structural formula is combined with a promoter preferably in the form of a salt.

  Patent Document 3 (Japanese Unexamined Patent Application Publication No. 2009-242794) discloses one or more scandium compounds selected from scandium alkoxides, halides and triflate compounds, metal alkoxides of titanium, zirconium, hafnium and cerium, and metals. A mixed catalyst system with one or more metal compounds selected from halides and metal halide alkoxides is described.

  Non-Patent Document 5 (L. Vogdanis, W. Heitz, Makromol. Chem., Rapid Commun. 7, 543 (1986)) describes that ring-opening polymerization of cyclic carbonate is performed using tetravalent tin. Non-Patent Document 6 (J. Choi, K. Kohno, Y. Ohshima, H. Yasuda, T. Sakakura, Catal. Commun. 9, 1630 (2008)) uses tetravalent tin from epoxide and carbon dioxide. The synthesis of cyclic carbonates is described.

US Pat. No. 3,585,168 US Patent Application Publication No. 2006/0089252 Japanese Patent Application Laid-Open No. 2009-242794

J. Controlled Release, 1997, 49, 263 H. Koinuma and H. Hirai, Makromol. Chem., 178, 1283-1294 (1977) W. Kuran, T. Listos, M. Abramczyk, and A. Dawidek, J. Macromol. Sci., Pure Appl. Chem., A35, 427-437 (1998) D. J. Darensbourg, E. L. Maynard, M. W. Holtcamp, K. K. Klausmeyer, and J. H. Reibenspies, Inorg. Chem., 35, 2682-2684 (1996) L. Vogdanis, W. Heitz, Makromol. Chem., Rapid Commun. 7, 543 (1986) J. Choi, K. Kohno, Y. Ohshima, H. Yasuda, T. Sakakura, Catal. Commun. 9, 1630 (2008)

  The present invention provides a method for producing a polycarbonate using a metal complex. The present invention also provides metal complexes and catalyst systems comprising metal complexes that are useful for producing polycarbonates from epoxide compounds and carbon dioxide.

  The present invention is the first example of realizing an alternating copolymerization of epoxide and carbon dioxide using a metal complex containing a tetravalent metal. Hereinafter, typical embodiments of the present invention will be listed, but the present invention is not limited thereto.

  A bivalent or trivalent tetradentate coordinated to the tetravalent metal by one or more types of heteroatoms selected from the group consisting of a 1.4valent metal and nitrogen, oxygen, sulfur and phosphorus A method for producing a polycarbonate, comprising copolymerizing an epoxide compound and carbon dioxide in the presence of a metal complex containing a ligand.

または、式（IV）：

（式中、Ｒ¹、Ｒ²、およびＲ³は、それぞれ独立して、水素原子、置換または非置換のアルキル基、置換または非置換のアルケニル基、置換または非置換のシクロアルキル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基、置換または非置換のアルコキシ基、置換または非置換のアシル基、置換または非置換のアシルオキシ基、置換または非置換のアルコキシカルボニル基、置換または非置換のアリールオキシカルボニル基、置換または非置換のアラルキルオキシカルボニル基、および置換または非置換のアミノ基からなる群から選択されるか、あるいは隣り合う炭素原子上の２個のＲ²および／または隣り合う炭素原子上の２個のＲ³が、互いに結合して置換または非置換の脂肪族環または芳香族環を形成してもよく；Ｒ⁴およびＲ⁵は、それぞれ独立して、水素原子、置換または非置換のアルキル基、置換または非置換のアルケニル基、置換または非置換のシクロアルキル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基、ハロゲノ基、ニトロ基、置換または非置換のアミノ基、およびシアノ基からなる群から選択されるか、あるいは隣り合う炭素原子上の２個のＲ⁵が、互いに結合して置換または非置換の脂肪族環または芳香族環を形成してもよく；Ｍは、チタン、ジルコニウム、ハフニウム、ルテニウム、オスミウム、白金、スズ、鉛、ゲルマニウムおよびセリウムからなる群から選択される４価金属であり；ＸおよびＺは、それぞれ独立して、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、およびアリールオキシドからなる群から選択されるアニオン性配位子である。）で表される、項目１に記載の方法。 2. The metal complex has the formula (I):

Or formula (IV):

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or Selected from the group consisting of an unsubstituted aryloxycarbonyl group, a substituted or unsubstituted aralkyloxycarbonyl group, and a substituted or unsubstituted amino group, or two R ² and / or on adjacent carbon atoms two R ³ on adjacent carbon atoms, also form a substituted or unsubstituted aliphatic or aromatic ring bonded to each other Ku; R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, Selected from the group consisting of a substituted or unsubstituted heteroaryl group, a halogeno group, a nitro group, a substituted or unsubstituted amino group, and a cyano group, or two R ⁵ on adjacent carbon atoms are They may combine to form a substituted or unsubstituted aliphatic or aromatic ring; M is selected from the group consisting of titanium, zirconium, hafnium, ruthenium, osmium, platinum, tin, lead, germanium and cerium. X and Z are each independently F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate, aromatic carbon 2. An anionic ligand selected from the group consisting of boxylates, alkoxides, and aryloxides).

または、式（V）：

（式中、Ｍは、チタン、ジルコニウム、ハフニウム、スズ、ゲルマニウムおよびルテニウムからなる群から選択される４価金属であり；ＸおよびＺは、それぞれ独立して、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、およびアリールオキシドからなる群から選択されるアニオン性配位子である。）で表される、項目２に記載の方法。 3. The metal complex has the formula (III):

Or the formula (V):

Wherein M is a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, tin, germanium and ruthenium; X and Z are each independently F ⁻ , Cl ⁻ , Br ⁻ , The method according to Item 2, wherein the anionic ligand is selected from the group consisting of I ⁻ , N ₃ ⁻ , aliphatic carboxylate, aromatic carboxylate, alkoxide, and aryloxide.

（式中、Ｒ⁶は、それぞれ独立して、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、または置換もしくは非置換の炭素数６〜２０のアリール基であり；Ｒ⁷は、イミダゾリウム環の炭素上の０〜３個の置換基であって、それぞれ独立して、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、または置換もしくは非置換の炭素数６〜２０のアリール基である。）からなる群から選択されるリンおよび／または窒素を含むカチオンと、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、およびアリールオキシドからなる群から選択されるアニオンとの塩からなる助触媒を前記金属錯体と組み合わせて用いて、エポキシド化合物と二酸化炭素を共重合させることを特徴とする、項目１〜３のいずれか１つに記載の方法。 4). [R ⁶ ₄ N] ⁺ , [R ⁶ ₄ P] ⁺ , [R ⁶ ₃ P = N = PR ⁶ ₃ ] ⁺ and formula (VI):

(In the formula, each R ⁶ is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; R ⁷ is 0 to 3 substituents on the carbon of the imidazolium ring, each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or substituted or unsubstituted And a cation containing phosphorus and / or nitrogen selected from the group consisting of F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate An epoxide compound and carbon dioxide are copolymerized using a promoter comprising a salt with an anion selected from the group consisting of aromatic carboxylate, alkoxide, and aryloxide in combination with the metal complex. Characterized Rukoto A method according to any one of items 1-3.

（式中、Ｒ⁶は、それぞれ独立して、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、または置換もしくは非置換の炭素数６〜２０のアリール基であり；Ｒ⁷は、イミダゾリウム環の炭素上の０〜３個の置換基であって、それぞれ独立して、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、または置換もしくは非置換の炭素数６〜２０のアリール基である。）からなる群から選択されるリンおよび／または窒素を含むカチオンと、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、およびアリールオキシドからなる群から選択されるアニオンとの塩からなる助触媒と、
を含む、触媒システム。 5. Bivalent or trivalent tetradentate coordinated to the tetravalent metal by one or more kinds of heteroatoms selected from the group consisting of a tetravalent metal and nitrogen, oxygen, sulfur and phosphorus A metal complex containing a ligand;
[R ⁶ ₄ N] ⁺ , [R ⁶ ₄ P] ⁺ , [R ⁶ ₃ P = N = PR ⁶ ₃ ] ⁺ and formula (VI):

(In the formula, each R ⁶ is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; R ⁷ is 0 to 3 substituents on the carbon of the imidazolium ring, each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or substituted or unsubstituted And a cation containing phosphorus and / or nitrogen selected from the group consisting of F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate A promoter comprising a salt with an anion selected from the group consisting of: an aromatic carboxylate, an alkoxide, and an aryloxide;
Including a catalyst system.

または、式（IV）：

（式中、Ｒ¹、Ｒ²、およびＲ³は、それぞれ独立して、水素原子、置換または非置換のアルキル基、置換または非置換のアルケニル基、置換または非置換のシクロアルキル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基、置換または非置換のアルコキシ基、置換または非置換のアシル基、置換または非置換のアシルオキシ基、置換または非置換のアルコキシカルボニル基、置換または非置換のアリールオキシカルボニル基、置換または非置換のアラルキルオキシカルボニル基、および置換または非置換のアミノ基からなる群から選択されるか、あるいは隣り合う炭素原子上の２個のＲ²および／または隣り合う炭素原子上の２個のＲ³が、互いに結合して置換または非置換の脂肪族環または芳香族環を形成してもよく；Ｒ⁴およびＲ⁵は、それぞれ独立して、水素原子、置換または非置換のアルキル基、置換または非置換のアルケニル基、置換または非置換のシクロアルキル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基、ハロゲノ基、ニトロ基、置換または非置換のアミノ基、およびシアノ基からなる群から選択されるか、あるいは隣り合う炭素原子上の２個のＲ⁵が、互いに結合して置換または非置換の脂肪族環または芳香族環を形成してもよく；Ｍは、チタン、ジルコニウム、ハフニウム、ルテニウム、オスミウム、白金、スズ、鉛、ゲルマニウムおよびセリウムからなる群から選択される４価金属であり；ＸおよびＺは、それぞれ独立して、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、およびアリールオキシドからなる群から選択されるアニオン性配位子である。）で表される、項目５に記載の触媒システム。 6). The metal complex has the formula (I):

Or formula (IV):

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or Selected from the group consisting of an unsubstituted aryloxycarbonyl group, a substituted or unsubstituted aralkyloxycarbonyl group, and a substituted or unsubstituted amino group, or two R ² and / or on adjacent carbon atoms two R ³ on adjacent carbon atoms, also form a substituted or unsubstituted aliphatic or aromatic ring bonded to each other Ku; R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, Selected from the group consisting of a substituted or unsubstituted heteroaryl group, a halogeno group, a nitro group, a substituted or unsubstituted amino group, and a cyano group, or two R ⁵ on adjacent carbon atoms are They may combine to form a substituted or unsubstituted aliphatic or aromatic ring; M is selected from the group consisting of titanium, zirconium, hafnium, ruthenium, osmium, platinum, tin, lead, germanium and cerium. X and Z are each independently F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate, aromatic carbon 6. The catalyst system according to item 5, which is an anionic ligand selected from the group consisting of a boxylate, an alkoxide, and an aryloxide.

または、式（V）：

（式中、Ｍは、チタン、ジルコニウム、ハフニウム、スズ、ゲルマニウムおよびルテニウムからなる群から選択される４価金属であり；ＸおよびＺは、それぞれ独立して、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、およびアリールオキシドからなる群から選択されるアニオン性配位子である。）で表される、項目６に記載の触媒システム。 7). The metal complex has the formula (III):

Or the formula (V):

Wherein M is a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, tin, germanium and ruthenium; X and Z are each independently F ⁻ , Cl ⁻ , Br ⁻ , The catalyst system according to item 6, wherein the catalyst system is an anionic ligand selected from the group consisting of I ⁻ , N ₃ ⁻ , aliphatic carboxylate, aromatic carboxylate, alkoxide, and aryloxide. .

（式中、Ｒ¹、Ｒ²、およびＲ³は、それぞれ独立して、水素原子、置換または非置換のアルキル基、置換または非置換のアルケニル基、置換または非置換のシクロアルキル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基、置換または非置換のアルコキシ基、置換または非置換のアシル基、置換または非置換のアシルオキシ基、置換または非置換のアルコキシカルボニル基、置換または非置換のアリールオキシカルボニル基、置換または非置換のアラルキルオキシカルボニル基、および置換または非置換のアミノ基からなる群から選択されるか、あるいは隣り合う炭素原子上の２個のＲ²および／または隣り合う炭素原子上の２個のＲ³が、互いに結合して置換または非置換の脂肪族環または芳香族環を形成してもよく；Ｍは、チタン、ジルコニウム、ハフニウム、ルテニウム、オスミウム、白金、スズ、鉛、ゲルマニウムおよびセリウムからなる群から選択される４価金属であり；Ｚは、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、およびアリールオキシドからなる群から選択されるアニオン性配位子である。）で表される、金属錯体。 8). Formula (I):

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or Selected from the group consisting of an unsubstituted aryloxycarbonyl group, a substituted or unsubstituted aralkyloxycarbonyl group, and a substituted or unsubstituted amino group, or two R ² and / or on adjacent carbon atoms two R ³ on adjacent carbon atoms, also form a substituted or unsubstituted aliphatic or aromatic ring bonded to each other Ku; M is titanium, zirconium, hafnium, ruthenium, osmium, platinum, tin, be a tetravalent metal selected lead, from the group consisting of germanium and cerium; Z ^{is, F -, Cl -, Br} -, I ^-, N ₃ ^-., aliphatic carboxylate, aromatic carboxylate, represented by alkoxide, and is an anionic ligand selected from the group consisting of aryloxides), a metal complex.

（式中、Ｒ¹およびＲ³は、それぞれ独立して、水素原子、置換または非置換のアルキル基、置換または非置換のアルケニル基、置換または非置換のシクロアルキル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基、置換または非置換のアルコキシ基、置換または非置換のアシル基、置換または非置換のアシルオキシ基、置換または非置換のアルコキシカルボニル基、置換または非置換のアリールオキシカルボニル基、置換または非置換のアラルキルオキシカルボニル基、および置換または非置換のアミノ基からなる群から選択され；Ｍは、チタン、ジルコニウム、ハフニウム、ルテニウム、オスミウム、白金、スズ、鉛、ゲルマニウムおよびセリウムからなる群から選択される４価金属であり；Ｚは、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、およびアリールオキシドからなる群から選択されるアニオン性配位子である。）で表される、項目８に記載の金属錯体。 9. Formula (II):

Wherein R ¹ and R ³ are each independently a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl Group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl Selected from the group consisting of an oxycarbonyl group, a substituted or unsubstituted aralkyloxycarbonyl group, and a substituted or unsubstituted amino group; M is titanium, zirconium, hafnium, ruthenium, osmium, platinum, tin, lead, germanium and A tetravalent metal selected from the group consisting of cerium; Z is F ⁻ , Cl ^−. , Br ⁻ , I ⁻ , N ₃ ⁻ , an anionic ligand selected from the group consisting of aliphatic carboxylates, aromatic carboxylates, alkoxides, and aryloxides). The metal complex described.

（式中、Ｍは、チタン、ジルコニウム、ハフニウム、スズ、ゲルマニウムおよびルテニウムからなる群から選択される４価金属であり；Ｚは、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、およびアリールオキシドからなる群から選択されるアニオン性配位子である。）で表される、項目９に記載の金属錯体。 10. Formula (III):

Wherein M is a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, tin, germanium and ruthenium; Z is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , 10. An anionic ligand selected from the group consisting of an aliphatic carboxylate, an aromatic carboxylate, an alkoxide, and an aryloxide.

  The present invention realizes alternating copolymerization of epoxide and carbon dioxide using a metal complex containing a tetravalent metal, and such a reaction has not been reported so far. Moreover, according to this invention, the catalyst system suitable for manufacture of a polycarbonate containing the metal complex containing a tetravalent metal and a promoter is provided. Furthermore, the present invention provides novel metal complexes that are particularly useful for producing polycarbonates from epoxides and carbon dioxide.

  The above description should not be construed as disclosing all embodiments of the present invention and all advantages related to the present invention.

  Hereinafter, the present invention will be described in more detail for the purpose of illustrating representative embodiments of the present invention, but the present invention is not limited to these embodiments.

  The method for producing a polycarbonate of the present invention is tetradentately coordinated to a tetravalent metal by one or more kinds of heteroatoms selected from the group consisting of a tetravalent metal and nitrogen, oxygen, sulfur and phosphorus. A metal complex containing a divalent or trivalent tetradentate ligand is used.

  Any metal can be used as the tetravalent metal as the metal center of the metal complex as long as it can take tetravalence, and suitable metals include the valence of the tetradentate ligand, the skeleton, It can be selected in consideration of conformation, substituents on the tetradentate ligand, and the like. As such a metal, for example, a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, ruthenium, osmium, platinum, tin, lead, germanium and cerium, or titanium, zirconium, hafnium, ruthenium, osmium, platinum , Tetravalent metals selected from the group consisting of tin, lead, and cerium. In some embodiments, the tetravalent metal is selected from the group consisting of titanium, zirconium, hafnium, tin, germanium and ruthenium, or the group consisting of titanium, zirconium, hafnium and ruthenium. In another embodiment, the tetravalent metal is selected from the group consisting of titanium and germanium. In another embodiment, the tetravalent metal is titanium. In yet another embodiment, the tetravalent metal is ruthenium.

  The metal complex includes a divalent or trivalent tetradentate ligand in which a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus is coordinated with the tetravalent metal described above. In this tetradentate ligand, the heteroatoms coordinated to the tetravalent metal may be the same or different combinations. The tetradentate ligand may be planar tetradentate with respect to the central metal, or may be coordinated such that the metal complex has a cis-α structure or a cis-β structure. When the tetradentate ligand is divalent, that is, a divalent anionic ligand, since the central metal is tetravalent, two monovalent anionic monodentate ligands are provided so as to balance the charge, Alternatively, a divalent anionic bidentate ligand can be further coordinated to the central metal. When the tetradentate ligand is trivalent, that is, a trivalent anionic ligand, one monovalent anionic monodentate ligand is further coordinated to the central metal so as to achieve a similar charge balance. be able to. Although not shown in the formula, a neutral ligand known to those skilled in the art may be further coordinated to the central metal.

で表すことができる。 The metal complex of one embodiment of the present invention has the following formula (I):

Can be expressed as

In formula (I), R ¹ , R ² , and R ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, A substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkoxycarbonyl group, Selected from the group consisting of a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted aralkyloxycarbonyl group, and a substituted or unsubstituted amino group, or two R ² on adjacent carbon atoms and And / or two R ³ on adjacent carbon atoms are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic ring. Also good.

The substituted or unsubstituted alkyl group for R ¹ , R ² , and R ³ is preferably a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably 1 to 1 carbon atoms. 6 linear or branched substituted or unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. It is done. The alkyl group is, for example, 1 or 2 selected from an alkoxy group, amino group, acyl group, acyloxy group, alkoxycarbonyl group, sulfanyl group, cyano group, nitro group, sulfo group, formyl group, halogeno group, aryl group and the like. It may be substituted with the above substituents.

The substituted or unsubstituted alkenyl group for R ¹ , R ² , and R ³ is preferably a linear or branched alkenyl group having 2 to 10 carbon atoms, more preferably a linear or branched chain alkenyl group having 2 to 6 carbon atoms. Examples include branched alkenyl groups such as vinyl group and 2-propenyl group. The alkenyl group is, for example, 1 or 2 selected from an alkoxy group, amino group, acyl group, acyloxy group, alkoxycarbonyl group, sulfanyl group, cyano group, nitro group, sulfo group, formyl group, halogeno group, aryl group and the like. It may be substituted with the above substituents.

The substituted or unsubstituted cycloalkyl group of R ¹ , R ² , and R ³ is preferably a cycloalkyl group having 3 to 10 carbon atoms, more preferably a cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl. Group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. The cycloalkyl group is selected from, for example, an alkoxy group, an amino group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a sulfanyl group, a cyano group, a nitro group, a sulfo group, a formyl group, a halogeno group, an aryl group, and the like. It may be substituted with two or more substituents.

The aryl group for R ¹ , R ² , and R ³ is preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, such as a substituted or unsubstituted aryl group such as a phenyl group, a naphthyl group, or a biphenyl group. Is mentioned. The aryl group includes, for example, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, alkyl groups such as tert-butyl groups, alkoxy groups such as methoxy groups and ethoxy groups, amino groups It may be substituted with one or more substituents selected from a group, acyl group, acyloxy group, alkoxycarbonyl group, sulfanyl group, cyano group, nitro group, sulfo group, formyl group, halogeno group and the like.

The substituted or unsubstituted heteroaryl group for R ¹ , R ² , and R ³ is preferably a substituted or unsubstituted heteroaryl group having 5 to 10 carbon atoms, such as a furyl group, a thienyl group, a pyridyl group, or pyrrolyl. And substituted or unsubstituted heteroaryl groups such as a group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, pyrimidyl group, pyridazinyl group, pyralidinyl group, quinolyl group, and isoquinolyl group. The heteroaryl group is, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group or a tert-butyl group, an alkoxy group such as a methoxy group or an ethoxy group, It may be substituted with one or more substituents selected from an amino group, acyl group, acyloxy group, alkoxycarbonyl group, sulfanyl group, cyano group, nitro group, sulfo group, formyl group, halogeno group and the like.

The substituted or unsubstituted alkoxy group for R ¹ , R ² , and R ³ is preferably a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, an n-butoxy group, n -Octyloxy group, cyclopentyloxy group, cyclohexyloxy group, cyclooctyloxy group, adamantyloxy group, tert-butoxy group and the like can be mentioned. The alkoxy group is, for example, 1 or 2 selected from an alkoxy group, amino group, acyl group, acyloxy group, alkoxycarbonyl group, sulfanyl group, cyano group, nitro group, sulfo group, formyl group, halogeno group, aryl group and the like. It may be substituted with the above substituents.

The substituted or unsubstituted acyl group for R ¹ , R ² , and R ³ is preferably an acyl group having 1 to 20 carbon atoms, such as a formyl group, an acetyl group, a trifluoroacetyl group, a propionyl group, a butyryl group, Aliphatic acyl groups such as isobutyryl group and pivaloyl group, benzoyl group, 3,5-dimethylbenzoyl group, 2,4,6-trimethylbenzoyl group, 2,6-dimethoxybenzoyl group, 2,4,6-trimethoxybenzoyl Groups, arylacyl groups such as 2,6-diisopropoxybenzoyl group, 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, 9-anthrylcarbonyl group and the like. The acyl group is, for example, 1 or 2 selected from an alkoxy group, amino group, acyl group, acyloxy group, alkoxycarbonyl group, sulfanyl group, cyano group, nitro group, sulfo group, formyl group, halogeno group, aryl group and the like. It may be substituted with the above substituents.

As the substituted or unsubstituted acyloxy group for R ¹ , R ² , and R ³ , an acyloxy group having 2 to 20 carbon atoms is preferable. For example, an acetoxy group, a trifluoroacetoxy group, a propionyloxy group, a butyryloxy group, an isobutyoxy group Aliphatic acyloxy groups such as ryloxy groups and pivaloyloxy groups, benzoyloxy groups, 3,5-dimethylbenzoyloxy groups, 2,4,6-trimethylbenzoyloxy groups, 2,6-dimethoxybenzoyloxy groups, 2,4,4 Examples include arylacyloxy groups such as 6-trimethoxybenzoyloxy group, 2,6-diisopropoxybenzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group, and 9-anthrylcarbonyloxy group. The acyloxy group is, for example, 1 or 2 selected from an alkoxy group, an amino group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a sulfanyl group, a cyano group, a nitro group, a sulfo group, a formyl group, a halogeno group, and an aryl group. It may be substituted with the above substituents.

The substituted or unsubstituted alkoxycarbonyl group for R ¹ , R ² , and R ³ is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, n- Examples include butoxycarbonyl group, n-octyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, cyclooctyloxycarbonyl group, adamantyloxycarbonyl group, and tert-butoxycarbonyl group. The alkoxycarbonyl group is selected from, for example, an alkoxy group, an amino group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a sulfanyl group, a cyano group, a nitro group, a sulfo group, a formyl group, a halogeno group, an aryl group, and the like. It may be substituted with two or more substituents.

The substituted or unsubstituted aryloxycarbonyl group for R ¹ , R ² , and R ³ is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms, such as a phenoxycarbonyl group or a naphthoxycarbonyl group. And biphenyloxycarbonyl group. The aryloxycarbonyl group is, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group, or an alkoxy group such as a methoxy group or an ethoxy group. , An amino group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a sulfanyl group, a cyano group, a nitro group, a sulfo group, a formyl group, a halogeno group and the like, may be substituted with one or more substituents .

The substituted or unsubstituted aralkyloxycarbonyl group for R ¹ , R ² , and R ³ is preferably an aralkyloxycarbonyl group having 8 to 20 carbon atoms, and examples thereof include a benzyloxycarbonyl group and a phenethyloxycarbonyl group. . Aralkyloxycarbonyl groups include, for example, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl groups, and alkoxy groups such as methoxy and ethoxy groups. Substituted with one or more substituents selected from amino group, acyl group, acyloxy group, alkoxycarbonyl group, sulfanyl group, cyano group, nitro group, sulfo group, formyl group, halogeno group, aryl group, etc. May be.

Examples of the substituted or unsubstituted amino group for R ¹ , R ² , and R ³ include an unsubstituted amino group (—NH ₂ ), an alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. And an amino group substituted with one or two substituents selected from the group consisting of aryl groups having 6 to 20 carbon atoms, such as a methylamino group, Examples thereof include a dimethylamino group, an ethylamino group, a diethylamino group, a cyclohexylamino group, a phenylamino group, and a diphenylamino group. The substituent on the nitrogen atom of the substituted amino group is, for example, an alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, methoxy group, One or more selected from alkoxy groups such as ethoxy groups, amino groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, sulfanyl groups, cyano groups, nitro groups, sulfo groups, formyl groups, halogeno groups, aryl groups, etc. It may be further substituted with a substituent.

Two R ² on adjacent carbon atoms and / or two R ³ on adjacent carbon atoms may be bonded to each other to form a substituted or unsubstituted aliphatic ring or aromatic ring. In this case, it is preferable to form a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms or a substituted or unsubstituted aromatic ring having 6 to 10 carbon atoms. Such an aliphatic ring or aromatic ring forms a condensed ring structure with the pyrrole ring part or benzene ring part of the tetradentate ligand. The ring thus formed is, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group or other alkyl group, methoxy group, ethoxy group, etc. Selected from aryl groups such as alkoxy groups, phenyl groups, tolyl groups, naphthyl groups, amino groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, sulfanyl groups, cyano groups, nitro groups, sulfo groups, formyl groups, halogeno groups, etc. Optionally substituted with one or more substituents.

  M in the metal complex of the formula (I) is a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, ruthenium, osmium, platinum, tin, lead, germanium and cerium, or titanium, zirconium, hafnium, ruthenium, A tetravalent metal selected from the group consisting of osmium, platinum, tin, lead and cerium, a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, tin, germanium and ruthenium, or titanium, zirconium, It is preferably a tetravalent metal selected from the group consisting of hafnium and ruthenium, more preferably a tetravalent metal selected from the group consisting of titanium and germanium, and even more preferably titanium (IV). .

Z is an anionic ligand selected from the group consisting of F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate, aromatic carboxylate, alkoxide, and aryloxide. Specific examples of Z include aliphatic carboxylates such as F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , acetate, trifluoroacetate, trichloroacetate, propionate, cyclohexylcarboxylate; benzoate, p- Methyl benzoate, 3,5-dichlorobenzoate, 3,5-bis (trifluoromethyl) benzoate, 4-dimethylaminobenzoate, 4-tert-butylbenzoate, pentafluorobenzoate, naphthalenecarboxylate, etc. Aromatic carboxylates; alkoxides such as methoxide, ethoxide, propoxide, isopropoxide; phenoxide, o-nitrophenoxide, p-nitrophenoxide, m-nitrophenoxide, 2,4-dinitrophenoxide, 3,5-dinitropheno Sid, 3,5-difluoro phenoxide, 3,5-bis (trifluoromethyl) phenoxide, 1-naphthoxide, and aryloxide such as 2-naphthoxide and the like. Z is preferably F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , alkoxide, or aryloxide.

で表されるものが挙げられる。Ｒ¹、Ｒ³、Ｍ、およびＺは上述したとおりである。 Specific examples of metal complexes of formula (I) include the following formula (II):

The thing represented by is mentioned. R ¹ , R ³ , M, and Z are as described above.

で表されるものが挙げられる。式中、Ｐｈはフェニル基を表し、^tＢｕはｔｅｒｔ−ブチル基を表し、Ｍは、チタン、ジルコニウム、ハフニウム、スズ、ゲルマニウムおよびルテニウムからなる群から選択される４価金属、またはチタン、ジルコニウム、ハフニウムおよびルテニウムからなる群から選択される４価金属、好ましくはチタンおよびゲルマニウムからなる群から選択される４価金属、さらに好ましくはチタン（IV）であり、Ｚは、上述したとおりであり、好ましくはイソプロポキシドまたはＣｌ^-である。 Furthermore, as a more specific example of the metal complex of the formula (I), the following formula (III):

The thing represented by is mentioned. In the formula, Ph represents a phenyl group, ^t Bu represents a tert-butyl group, M represents a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, tin, germanium, and ruthenium, or titanium, zirconium, A tetravalent metal selected from the group consisting of hafnium and ruthenium, preferably a tetravalent metal selected from the group consisting of titanium and germanium, more preferably titanium (IV), and Z is as described above, preferably the isopropoxide or Cl ^- is.

で表すことができる。この金属錯体は、いわゆるポルフィリン骨格を有する四座配位子が金属中心Ｍに平面四座配位し、２つのアキシアル位に配位子Ｘが配位した構造を有している。 The metal complex used in another embodiment of the present invention has the following formula (IV):

Can be expressed as This metal complex has a structure in which a tetradentate ligand having a so-called porphyrin skeleton is planar tetradentately coordinated to the metal center M, and the ligand X is coordinated to two axial positions.

In formula (IV), R ⁴ and R ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Selected from the group consisting of aryl groups, substituted or unsubstituted heteroaryl groups, halogeno groups, nitro groups, substituted or unsubstituted amino groups, and cyano groups, or two Rs on adjacent carbon atoms ⁵ may be bonded to each other to form a substituted or unsubstituted aliphatic ring or aromatic ring.

R ⁴ and R ⁵ are a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. Descriptions and specific examples are as described above for R ¹ , R ² and R ³ of the metal complex of the formula (I).

Examples of the substituted or unsubstituted amino group for R ⁴ and R ⁵ include an unsubstituted amino group (—NH ₂ ), an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and the number of carbon atoms Examples include amino groups substituted with one or two substituents selected from the group consisting of 6 to 20 aryl groups. Examples of the substituted amino group include a methylamino group, a dimethylamino group, Examples thereof include an ethylamino group, a diethylamino group, a cyclohexylamino group, a phenylamino group, and a diphenylamino group. The substituent on the nitrogen atom of the substituted amino group is, for example, an alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, methoxy group, One or more selected from alkoxy groups such as ethoxy groups, amino groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, sulfanyl groups, cyano groups, nitro groups, sulfo groups, formyl groups, halogeno groups, aryl groups, etc. It may be further substituted with a substituent.

Two R ⁵ on adjacent carbon atoms may be bonded to each other to form a substituted or unsubstituted aliphatic ring or aromatic ring. In this case, the substituted or unsubstituted C 4-10 substituted or unsubstituted ring It is preferable to form an aliphatic ring or a substituted or unsubstituted aromatic ring having 6 to 10 carbon atoms. Such an aliphatic ring or aromatic ring forms a condensed ring structure with the pyrrole ring portion of the tetradentate ligand. The ring thus formed is, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group or other alkyl group, methoxy group, ethoxy group, etc. Selected from aryl groups such as alkoxy groups, phenyl groups, tolyl groups, naphthyl groups, amino groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, sulfanyl groups, cyano groups, nitro groups, sulfo groups, formyl groups, halogeno groups, etc. Optionally substituted with one or more substituents.

R ⁴ and R ⁵ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or two R ⁵ on adjacent carbon atoms. Are preferably bonded to each other to form a substituted or unsubstituted aliphatic ring or aromatic ring, more preferably R ⁴ is a substituted or unsubstituted aryl group, and R ⁵ is a hydrogen atom.

  M in the metal complex of the formula (IV) is a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, ruthenium, osmium, platinum, tin, lead, germanium and cerium, or titanium, zirconium, hafnium, ruthenium, A tetravalent metal selected from the group consisting of osmium, platinum, tin, lead and cerium, a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, tin, germanium and ruthenium, or titanium, zirconium, A tetravalent metal selected from the group consisting of hafnium and ruthenium is preferable, and ruthenium (IV) is more preferable.

Each X is independently an anionic coordination selected from the group consisting of F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate, aromatic carboxylate, alkoxide, and aryloxide. It is a child. Specific examples of X are as described above for Z of the metal complex of the formula (I). In addition, two Xs may be one bidentate ligand connected via a divalent linking group such as a substituted or unsubstituted alkylene group or an arylene group. In this case, the bidentate ligand is coordinated to the metal center M with an oxygen atom derived from a carboxylate group or a hydroxyl group. X is preferably F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , alkoxide, or aryloxide.

で表されるものが挙げられる。Ｐｈはフェニル基を表し、Ｍは、チタン、ジルコニウム、ハフニウム、スズ、ゲルマニウムおよびルテニウムからなる群から選択される４価金属、またはチタン、ジルコニウム、ハフニウムおよびルテニウムからなる群から選択される４価金属、好ましくはルテニウム（IV）であり、Ｘは、上述したとおりであり、好ましくはＣｌ^-である。 As a specific example of the metal complex of the formula (IV), the following formula (V):

The thing represented by is mentioned. Ph represents a phenyl group, and M is a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, tin, germanium and ruthenium, or a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium and ruthenium. preferably a ruthenium (IV), X is is as described above, preferably Cl ^- is.

  Another embodiment of the present invention is a catalyst system in which the above metal complex is combined with a cocatalyst, and the polycarbonate production method of the present invention may be carried out using such a catalyst system. Such a catalyst system is particularly useful for the production of polycarbonate by copolymerizing an epoxide compound and carbon dioxide, increasing the reaction rate of the copolymerization by using a cocatalyst in combination with the metal complex, and / or It is possible to increase the alternating regularity of the copolymer and / or suppress the formation of cyclic carbonate as a by-product.

（式中、Ｒ⁶は、上記説明したとおりであり、Ｒ⁷は、イミダゾリウム環の炭素上の０〜３個の置換基であって、それぞれ独立して、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、または置換もしくは非置換の炭素数６〜２０のアリール基である。）からなる群から選択されるリンおよび／または窒素を含むカチオンと、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、およびアリールオキシドからなる群から選択されるアニオンとの塩を使用できる。 An example of a cocatalyst that can be combined with the metal complex is a salt composed of a cation containing phosphorus and / or nitrogen and a counter anion. As such a cocatalyst, [R ⁶ ₄ N] ⁺ , [R ⁶ ₄ P] ⁺ , [R ⁶ ₃ P = N = PR ⁶ ₃ ] ⁺ (wherein R ⁶ independently represents carbon An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms) and formula (VI):

(In the formula, R ⁶ is as described above, and R ⁷ is 0 to 3 substituents on carbon of the imidazolium ring, and each independently represents an alkyl group having 1 to 20 carbon atoms. A cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms) and a cation containing phosphorus and / or nitrogen selected from F ⁻ , Cl ^{-, Br -, I -,} N 3 -, aliphatic carboxylate, aromatic carboxylate, alkoxide, and the salts of anions selected from the group consisting of aryloxides may be used.

Specific examples of R ⁶ and R ⁷ include methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group. , A heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, etc., a linear or branched alkyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group; a phenyl group And substituted or unsubstituted aryl groups such as o-tolyl group, m-tolyl group, p-tolyl group, 2,6-xylyl group, mesityl group, 1-naphthyl group, 2-naphthyl group and anthryl group. . R ⁶ and R ⁷ are all the above cations ([R ⁶ ₄ N] ⁺ , [R ⁶ ₄ P] ⁺ , [R ⁶ ₃ P = N = PR ⁶ ₃ ] ⁺ , imidazolium of the formula (VI)) Can be selected and combined so as to exert a steric effect advantageous to the copolymerization reaction, that is, to have an appropriate bulkiness.

As the cation constituting the salt, [R ⁶ ₄ N] ⁺ , [R ⁶ ₃ P = N = PR ⁶ ₃ ] ⁺ , or imidazolium of the formula (VI) is preferably used, and [R ⁶ ₃ P = N = PR ⁶ ₃ ] ⁺ is more preferred.

Specific examples of the quaternary ammonium [R ⁶ ₄ N] ⁺ include tetrabutylammonium, tetrahexylammonium, tricyclohexylmethylammonium, trimethylphenylammonium and the like.

Specific examples of the quaternary phosphonium [R ⁶ ₄ P] ⁺ include tetrabutylphosphonium, tetrahexylphosphonium, tetracyclohexylphosphonium, tetraphenylphosphonium, tetra (methoxyphenyl) phosphonium and the like.

Specific examples of bis (phosphoranylidene) ammonium [R ⁶ ₃ P═N═PR ⁶ ₃ ] ⁺ include bis (tributylphosphoranylidene) ammonium, bis (ethyldiphenylphosphoranylidene) ammonium, bis (n-butyldiphenylphosphorani). Ridene) ammonium, bis (dimethylphenylphosphoranylidene) ammonium, bis (triphenylphosphoranylidene) ammonium, bis (tolylphosphoranylidene) ammonium, bis (trinaphthylphosphoranylidene) ammonium and the like. Among these, bis (triphenylphosphoranylidene) ammonium is preferable.

  Specific examples of imidazoliums of formula (VI) include 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1,3-diethylimidazolium, 1-ethyl-2,3-dimethyl-imidazolium. 1-butyl-3-methylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1-hexyl-3-methylimidazolium and the like.

Examples of the anion constituting the salt include those described above with respect to Z. F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , acetate, trifluoroacetate, trichloroacetate, benzoate, or pentafluorobenzoate F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , trifluoroacetate, trichloroacetate, benzoate, or pentafluorobenzoate, and more preferably F ⁻ , Cl ⁻ , Br ^−. , I ⁻ , benzoate, or pentafluorobenzoate are particularly preferred.

Examples of the salt composed of the cation and the anion include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium acetate, tetrabutylphosphonium chloride, tetraphenylphosphonium chloride, bis (triphenylphosphoranylidene) ammonium fluoride (PPNF). ), Bis (triphenylphosphoranylidene) ammonium chloride (PPNCl), bis (triphenylphosphoranylidene) ammonium pentafluorobenzoate (PPNOBzF ₅ ), 1,3-dimethylimidazolium chloride, 1-ethyl-2,3 - dimethyl - imidazolium chloride can be mentioned, PPNF, it is PPNCl and PPNOBzF ₅ preferred.

（式中、Ｒ⁸およびＲ⁹は、同一でも異なっていてもよく、Ｈ、置換もしくは非置換のアルキル基、または置換もしくは非置換のアリール基であるか、またはＲ⁸とＲ⁹が互いに結合して置換もしくは非置換の環を形成してもよい。）で表されるものが使用できる。 As the epoxide compound used in the method for producing a polycarbonate of the present invention, the formula (VII):

(Wherein R ⁸ and R ⁹ may be the same or different and are H, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, or R ⁸ and R ⁹ are bonded to each other) To form a substituted or unsubstituted ring.) Can be used.

As the alkyl group for R ⁸ and R ⁹ , a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms is preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl Group, sec-butyl group, tert-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 2-hexyl group, 3- Hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 3,3-dimethyl-n- Butyl group, n-heptyl group, 2-heptyl group, 1-ethyl-1,2-dimethyl-n-propyl group, 1-ethyl-2,2-dimethyl-n-propyl group, n-octyl group, n- Noni Group, n-decyl group and the like, and a methyl group is preferable. The alkyl group is, for example, one or more substituents selected from an alkoxy group, amino group, alkoxycarbonyl group, acyloxy group, sulfanyl group, cyano group, nitro group, sulfo group, formyl group, halogeno group, aryl group and the like. May be substituted.

The substituted or unsubstituted aryl group for R ⁸ and R ⁹ is preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, such as a phenyl group, an indenyl group, or a naphthyl group. , Tetrahydronaphthyl group and the like, and a phenyl group is preferable. The aryl group is, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group or a tert-butyl group, or another aryl group such as a phenyl group or a naphthyl group. , An alkoxy group, an amino group, an alkoxycarbonyl group, an acyloxy group, a sulfanyl group, a cyano group, a nitro group, a sulfo group, a formyl group, a halogeno group and the like.

R ⁸ and R ⁹ may be bonded to each other to form a substituted or unsubstituted ring, and preferably a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms. For example, when R ⁸ and R ⁹ are bonded to each other via — (CH ₂ ) ₄ —, a cyclohexane ring is formed. The ring thus formed is, for example, an alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, phenyl group, naphthyl group, etc. Substituted with one or more substituents selected from aryl group, alkoxy group, amino group, alkoxycarbonyl group, acyloxy group, sulfanyl group, cyano group, nitro group, sulfo group, formyl group, halogeno group, etc. Also good.

  Examples of such epoxide compounds include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, and styrene oxide. , Cyclohexene oxide, 3-phenylpropylene oxide, 3,3,3-trifluoropropylene oxide, and the like, ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, or combinations thereof are preferable, ethylene oxide, propylene oxide, or a combination thereof. A combination is more preferred.

  The copolymerization of the epoxide compound and carbon dioxide can be carried out using a known polymerization reaction apparatus that can be pressurized, such as an autoclave. The reaction temperature for copolymerization can generally be about 0 ° C. or higher and about 120 ° C. or lower, preferably about 10 ° C. or higher and about 100 ° C. or lower, and is about 20 ° C. or higher and about 90 ° C. or lower. Is more preferable. When the reaction temperature is increased, the reaction rate increases and TOF can be improved.

  The partial pressure of carbon dioxide during copolymerization can be generally about 0.1 MPa or more and about 20 MPa or less, and preferably about 10 MPa or less. An inert gas such as nitrogen or argon may be present in the reaction atmosphere together with carbon dioxide.

  The molar ratio of the epoxide compound to the metal complex is generally about 100: 1 or more, about 200: 1 or more, or about 400: 1 or more, as the ratio of the epoxide compound to the metal complex. Efficiency can be increased. On the other hand, since the reaction time is generally longer when the complex concentration is low, the above molar ratio should be set to epoxide compound: metal element in metal complex = about 20,000: 1 or less, or about 10,000: 1 or less. Is common. The amount of cocatalyst used as needed can generally be about 0.1 to about 10 moles, and is about 0.5 to about 5 moles per mole of metal in the metal complex. Is more preferable, and it is more preferably about 0.8 to about 1.2 mol.

  Copolymerization may be performed without a solvent, or may be performed using a solvent as necessary. Usable solvents include, for example, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, amides such as dimethylformamide, ethers such as tetrahydrofuran and 1,2-dimethoxyethane, propylene carbonate, Carbonate solvents such as dimethyl carbonate and combinations thereof can be used, dichloromethane, toluene, dimethylformamide, tetrahydrofuran, 1,2-dimethoxyethane and combinations thereof are preferred, dichloromethane, tetrahydrofuran, 1,2-dimethoxyethane And combinations thereof are more preferred. When using a solvent, the amount thereof can generally be about 0.1 to about 100 parts by weight, preferably about 0.2 to about 50 parts by weight, based on 1 part by weight of the epoxide compound. More preferred is about 0.5 to about 20 parts by weight.

  After the desired amount of epoxide compound is polymerized, known post-treatment can be performed. For example, hydrochloric acid, methanol, hydrochloric acid / methanol mixture or the like can be added to the reaction mixture as a reaction terminator, and the reaction can be terminated by raising the temperature and / or stirring as necessary. Thereafter, for example, the polymer may be reprecipitated using methanol, hexane or the like as a poor solvent, and the complex may be extracted from the solid mixture using a Soxhlet extractor. In addition, the polymer may be further purified using a known means such as column chromatography.

The ¹ H-NMR spectrum and ¹³ C-NMR spectrum of the compound obtained in this example were measured using JNM-JNM-ECP500 or JNM-ECS400, or Bruker DPX-400. The IR spectrum was measured using FTIR-8400 manufactured by Shimadzu or FT / IR-410 manufactured by JASCO. The molecular weight of polycarbonate is measured by GL Science High Performance Liquid Chromatography System (DG660B / PU713 / UV702 / RI704 / CO631A) and SHODEX KF-804L column (when epoxide is ethylene oxide, K-804L column manufactured by SHODEX). ) Using two of them, tetrahydrofuran (chloroform when epoxide is ethylene oxide) as an eluent (40 ° C., 1.0 mL / min), measured based on polystyrene standards, and measured, and analysis software (manufactured by Scientific Software) It is determined by processing with EZChrom Elite), or a high performance liquid chromatography system (HLC-8220) manufactured by Tosoh Corporation and TSKgel SuperMultipore HZ- manufactured by Tosoh Corporation Using two M columns and two TSKgel SuperMultipore HZ-N columns respectively, tetrahydrofuran as an eluent (40 ° C., 0.5 mL / min), measurement based on polystyrene standards, and analysis software (manufactured by Tosoh Corporation) GPC-8020 model II).

  Compound 1 was synthesized according to the method described in the literature (Org. Lett. 2004, 6, 3981.). Compound 2 was a 99% grade purchased from Strem. Compound 3 was synthesized according to literature methods (Organometallics 2007, 26, 2957.). The Ru complex 9 represented by the following formula was synthesized according to a method described in the literature (Bioinorg. Chem. 1971 1, 57; Inorg. Chem. 2006, 45, 4769.).

1. 1. Synthesis of ligand precursor 1-1. Synthesis of Compound 4: Zinc chloride (II) (1.64 g, 12 mmol), sodium pyrrolide (1.07 g, 12 mmol), 1,4-dioxane (9 mL) in a glass Schlenk reaction tube (20 mL volume) under an argon atmosphere. ) And stirred at room temperature for 25 minutes. Palladium (II) acetate (9 mg, 0.04 mmol), compound 2 (12 mg, 0.04 mmol) and compound 3 (1.20 g, 4.0 mmol) were added, and the mixture was stirred at 100 ° C. for 46 hours. Diethyl ether (6 mL) and water (6 mL) were added to the resulting reaction solution, and the insoluble material was filtered off. The filtrate was transferred to a separatory funnel and extracted with diethyl ether (50 mL × 3). The collected organic layer was dried over anhydrous sodium sulfate. The desiccant was filtered off and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 20/1) to give compound 4. Yield: 368 mg. Yield: 40%. ¹ H-NMR (500 MHz, CDCl ₃ ) δ = 9.19 (s, 1H), 7.38 (d, J = 2.5 Hz, 1H), 7.25 (d, J = 2.5 Hz, 1H) 6.91-6.89 (m, 1H), 6.47-6.46 (m, 1H), 6.31-6.29 (m, 1H), 3.45 (s, 3H), 1 .44 (s, 1 H), 1.34 (s, 1 H); ¹³ C-NMR (125 MHz, CDCl ₃ ) δ = 153.8, 146.1, 142.3, 130.3, 126.0, 124 6, 122.8, 118.2, 108.8, 106.8, 60.5, 35.5, 34.7, 31.7, 31.2.

1-2. Synthesis of Compound 5: Compound 4 (3.06 g, 10.7 mmol), benzaldehyde (0.55 mL, 5.4 mmol), and dichloromethane (280 mL) were placed in a glass Schlenk reaction tube (1,000 mL volume) under an argon atmosphere. While stirring, trifluoroacetic acid (0.12 mL, 1.6 mmol) was added. After stirring at room temperature for 4.5 hours, 2,3-dichloro-5,6-dicyanoparabenzoquinone (DDQ, 1.22 g, 5.4 mmol) was added and stirred for 18 hours. The resulting reaction solution was washed with a saturated aqueous sodium hydrogen carbonate solution (50 mL × 4), and the organic layer was filtered through basic alumina and concentrated. The residue was purified by silica gel column chromatography (eluent: dichloromethane, then dichloromethane / ethyl acetate = 5/1) to obtain almost pure compound 5. Yield: 2.31 g. Yield: 33%. ¹ H-NMR (500 MHz, CDCl ₃ ) δ = 7.60-7.58 (m, 2H), 7.51 (d, J = 2.5 Hz, 2H), 7.48-7.46 (m, 3H), 7.34 (d, J = 2.5 Hz, 2H), 6.77 (d, J = 4.1 Hz, 2H), 6.62 (d, J = 4.1 Hz, 2H), 3. 63 (s, 6H), 1.42 (s, 18H), 1.31 (s, 18H); ¹³ C-NMR (125 MHz, CDCl ₃ ) δ = 156.2, 154.3, 145.5, 142 2, 141.5, 138.8, 138.1, 131.2, 128.9, 128.6, 127.7, 127.1, 125.2, 125.0, 119.1, 61.8 35.5, 34.7, 31.7, 31.2.

1-3. Synthesis of Ligand Precursor 6: Under argon atmosphere, sodium hydride (62 mg, 2.6 mmol) and dimethylformamide (10 mL) were placed in a glass Schlenk reaction tube (80 mL), and dodecanethiol (0.60 mL, 2 0.5 mmol) and stirred at room temperature for 1.5 hours. Compound 5 (329 mg, 0.50 mmol) was added as a solid and stirred at 110 ° C. for 8.5 hours. A saturated aqueous ammonium chloride solution (5 mL) was added to the resulting reaction solution, water (15 mL) was added, and the mixture was extracted with ethyl acetate (20 mL × 3). The collected organic layer was dried over anhydrous sodium sulfate. The desiccant was filtered off and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: hexane / dichloromethane = 5/1) to obtain a ligand precursor 6. Yield: 215 mg. Yield: 69%. ¹ H-NMR (500 MHz, CDCl ₃ ) δ = 7.56 (d, J = 2.1 Hz, 2H), 7.51-7.44 (m, 5H), 7.35 (d, J = 2. 1 Hz, 2H), 6.92 (d, J = 4.4 Hz, 2H), 6.62 (d, J = 4.4 Hz, 2H), 1.50 (s, 18H), 1.35 (s, 18 C); ¹³ C-NMR (125 MHz, CDCl ₃ ) δ = 154.9, 153.0, 142.0, 140.2, 139.0, 138.6, 136.1, 131.6, 130.1 , 128.9, 127.7, 125.5, 123.1, 118.2, 116.6, 35.0, 34.5, 31.7, 30.4.

2. 2. Synthesis of titanium complex 2-1. Synthesis of Titanium Complex 7: Under argon atmosphere, put Ligand Precursor 6 (50 mg, 0.080 mmol) and tetrahydrofuran (1 mL) in a glass vial, add sodium hydride (19 mg, 0.80 mmol), Stir at room temperature for 15 minutes. The resulting reaction solution was filtered through a syringe filter (Advantec DISMIC-13HP), and the filtrate was slowly added to titanium (IV) dichlorodiisopropoxide (20 mg, 0.084 mmol) in a separate glass vial. It was. After stirring at room temperature for 20 minutes, the mixture was concentrated under reduced pressure. Hexane (5 mL) was added and filtered through a syringe filter (DISMIC-13HP from Advantec). The filtrate was concentrated to obtain titanium complex 7. Yield 56 mg. Yield 95%. ¹ H-NMR (500 MHz, CDCl ₃ ) δ = 7.72 (d, J = 2.5 Hz, 2H), 7.45-7.40 (m, 5H), 7.34 (d, J = 2. 5 Hz, 2H), 7.02 (d, J = 4.6 Hz, 2H), 6.43 (d, J = 4.6 Hz, 2H), 4.52 (septet, J = 6.0 Hz, 1H), 1.61 (s, 18H), 1.35 (s, 18H), 0.76 (d, J = 6.0 Hz, 6H).

2-2. Synthesis of titanium complex 8: Under argon atmosphere, a ligand precursor 6 (71 mg, 0.11 mmol) and tetrahydrofuran (0.70 mL) were placed in a glass vial, and sodium hydride (27 mg, 1.1 mmol) was added. After that, the mixture was stirred at room temperature for 15 minutes. The resulting reaction solution was filtered through a syringe filter (DISMIC-13HP, manufactured by Advantec), washed with the filter using THF (4 mL), and the filtrates were transferred to another Schlenk reaction tube (20 mL). While stirring at −78 ° C., 0.13 mL of a methylene chloride solution (1M) of titanium (IV) tetrachloride was added, stirred at the same temperature for 20 minutes, and gradually warmed to room temperature. The mixture was concentrated under reduced pressure, diethyl ether (5 mL) was added, and the mixture was filtered through a syringe filter (DISMIC-13HP manufactured by Advantec). The filtrate was concentrated to obtain titanium complex 8. Yield 76 mg. Yield 95%. ¹ H-NMR (500 MHz, CDCl ₃ ) δ = 7.62 (d, J = 2.5 Hz, 2H), 7.53-7.50 (m, 1H), 7.46-7.44 (m, 2H), 7.41-7.37 (m, 2H), 7.32-7.29 (m, 3H), 6.84 (d, J = 4.4 Hz, 2H), 6.24 (d, J = 4.4 Hz, 2H), 1.56 (s, 18H), 1.33 (s, 18H).

3. Alternating copolymerization of propylene oxide and carbon dioxide (Example 1-5)
In an argon atmosphere, in a stainless steel 50 mL pressure resistant reaction vessel, Ti complex (7.2 × 10 ⁻³ mmol) and bis (triphenylphosphoranylidene) ammonium chloride (PPNCl) (4 mg, 7.2 ×) shown in Table 1 were used. 10 ⁻³ mmol) was added, propylene oxide (1.0 mL, 14 mmol) was added, and then carbon dioxide (2.0 MPa) was injected. The mixture was stirred at the temperature shown in Table 1 for 12 hours to remove carbon dioxide. The resulting polymerization solution was dissolved in deuterated chloroform, and phenanthrene was added as an internal standard. After uniformly dissolving, a small amount is extracted, and from ¹ H-NMR spectrum, the amount of propylene oxide incorporated into the copolymer per unit time and per unit amount of titanium [TOF, unit is mol · (Mol Ti) ^-1 · h ^-1 ], ratio of copolymer (PPC) to cyclic propylene carbonate (PC) (PPC / PC), carbonate linkage (carbonate) in the copolymer (%) and ether The bonding ratio (m: n) was estimated. The remaining polymerization product and NMR sample were combined and transferred to a glass flask using methylene chloride. 0.1 mL of a mixed solution of methanol and 1M hydrochloric acid (mixing ratio is methanol / 1M hydrochloric acid = 95/5) was added and stirred for 1 minute, followed by concentration. The resulting residue was dissolved in a small amount of methylene chloride and poured into methanol to precipitate a polymer. The number average molecular weight (M _n , g · mol ⁻¹ ) and molecular weight distribution (M _w / M _n ) of the obtained copolymer were estimated by high performance liquid chromatography.

4). Alternating copolymerization of cyclohexene oxide and carbon dioxide (Examples 6-8)
(1) Examples 6 and 7
In an argon atmosphere, a stainless steel 50 mL pressure resistant reactor was charged with the Ti complex (0.01 mmol) and PPNCl (6 mg, 0.01 mmol) shown in Table 2, and cyclohexene oxide (2.0 mL, 20 mmol) was added. Carbon dioxide (2.0 MPa) was injected. The mixture was stirred at 80 ° C. for 12 hours to remove carbon dioxide. The resulting polymerization solution was dissolved in deuterated chloroform, and phenanthrene was added as an internal standard. After dissolving uniformly, a small amount was extracted and a ¹ H-NMR spectrum was measured. The remaining polymerization product and NMR sample were combined and transferred to a glass flask using methylene chloride. 0.1 mL of a mixed solution of methanol and 1M hydrochloric acid (mixing ratio is methanol / 1M hydrochloric acid = 95/5) was added and stirred for 1 minute, followed by concentration. The ratio (PCHC / CHC) of copolymer (PCHC) to cyclic cyclohexene carbonate (CHC) was estimated from the IR spectrum, and from this result and the result of the NMR spectrum measurement, per unit time and per unit amount of titanium per unit amount of titanium. The amount of cyclohexene oxide incorporated into the copolymer [TOF, unit is mol · (mol Ti) ⁻¹ · h ⁻¹ ], carbonate linkage (%) and ether linkage of the copolymer in the copolymer The ratio (m: n) was estimated. The resulting residue was dissolved in a small amount of methylene chloride and poured into methanol to precipitate a polymer. The number average molecular weight (M _n , g · mol ⁻¹ ) and molecular weight distribution (M _w / M _n ) of the obtained copolymer were estimated by high performance liquid chromatography.

(2) Example 8
Under a nitrogen atmosphere, in a stainless steel 50 mL pressure resistant reaction vessel, Ru complex 9 (1.7 × 10 ⁻² mmol), PPNCl (10 mg, 1.7 × 10 ⁻² mmol), a 1: 1 solvent mixture of dichloromethane and tetrahydrofuran (0 .8 mL) was added, cyclohexene oxide (0.86 mL, 8.5 mmol) was added, and then carbon dioxide (5.0 MPa) was injected. The mixture was stirred at 80 ° C. for 24 hours to remove carbon dioxide. A part of the resulting polymerization solution was extracted, and the ratio (PCHC / CHC) of the copolymer (PCHC) and cyclic cyclohexene carbonate (CHC) was estimated from the IR spectrum. Further, together with the results of ¹ H-NMR spectrum measurement, the amount of cyclohexene oxide incorporated in the copolymer per unit time and per unit amount of Ru [TOF, the unit is mol · (mol Ru ⁻¹ · h ⁻¹ ], the ratio of carbonate linkage (%) and ether linkage (m: n) in the copolymer was estimated. 1 mL of a mixed solution of methanol and 1M hydrochloric acid (mixing ratio: methanol / 1M hydrochloric acid = 95/5) was added to the remaining polymerization product and stirred for 5 minutes. A small amount of chloroform was added here for dilution, and the entire amount was poured into methanol to precipitate a polymer. The number average molecular weight (M _n , g · mol ⁻¹ ) and molecular weight distribution (M _w / M _n ) of the obtained copolymer were estimated by high performance liquid chromatography.

5. Alternating copolymerization of ethylene oxide and carbon dioxide (Example 9)
In an argon atmosphere, a 50 mL pressure-resistant reaction vessel made of stainless steel was charged with Ti complex (7.2 × 10 ⁻³ mmol) and PPNCl (4 mg, 7.2 × 10 ⁻³ mmol) shown in Table 3 and ethylene oxide (0. 7 mL, 14 mmol) was added, and carbon dioxide (2.0 MPa) was injected. The mixture was stirred at 60 ° C. for 12 hours to remove carbon dioxide. The resulting polymerization solution was dissolved in deuterated chloroform, and phenanthrene was added as an internal standard. After uniformly dissolving, a small amount is extracted, and from the ¹ H-NMR spectrum, the amount of ethylene oxide incorporated in the copolymer per unit time and per unit amount of titanium [TOF, the unit is mol · mol (Mol Ti) ⁻¹ · h ⁻¹ ], ratio of copolymer (PEC) to cyclic ethylene carbonate (EC) (PEC / EC), carbonate linkage in the copolymer (carbonate linkage,%) and ether linkage The ratio (m: n) was estimated. The remaining polymerization product and NMR sample were combined and transferred to a glass flask using methylene chloride. 0.1 mL of a mixed solution of methanol and 1M hydrochloric acid (mixing ratio is methanol / 1M hydrochloric acid = 95/5) was added and stirred for 1 minute, followed by concentration. The number average molecular weight (M _n , g · mol ⁻¹ ) and molecular weight distribution (M _w / M _n ) of the obtained copolymer were estimated by high performance liquid chromatography.

6). Synthesis of Zirconium Complex 10: Under an argon atmosphere, a ligand precursor 6 (31 mg, 0.050 mmol) and tetrahydrofuran (1 mL) were placed in a glass vial, sodium hydride (9 mg, 0.36 mmol) was added, Stir at room temperature for 40 minutes. The resulting reaction solutions were filtered through a syringe filter (Advantec DISMIC-13HP), washed with THF (2.5 mL), and the filtrates were transferred to another glass vial. Zirconium (IV) tetrachloride (13 mg, 0.056 mmol) was added with stirring at room temperature, and the mixture was stirred at room temperature for 3 hours and then concentrated under reduced pressure. Diethyl ether (5 mL) was added and filtered through a syringe filter (DISMIC-13HP manufactured by Advantec). The filtrate was concentrated to obtain zirconium complex 10 quantitatively. Yield 44.4 mg. ¹ H-NMR (500 MHz, THF-d8) δ = 7.68 (d, J = 2.3 Hz, 2H), 7.51-7.30 (m, 7H), 6.99 (d, J = 4 .4 Hz, 2H), 6.42 (d, J = 4.4 Hz, 2H), 1.52 (s, 18H), 1.30 (s, 18H).

7). Synthesis of Hafnium Complex 11: Under argon atmosphere, ligand precursor 6 (32 mg, 0.050 mmol) and tetrahydrofuran (0.5 mL) were placed in a glass vial, and sodium hydride (8 mg, 0.32 mmol) was added. Then, it stirred at room temperature for 1 hour. The resulting reaction solutions were filtered through a syringe filter (Advantec DISMIC-13HP), washed with THF (2.5 mL), and the filtrates were transferred to another glass vial. Hafnium (IV) tetrachloride (18 mg, 0.055 mmol) was added with stirring at room temperature, and the mixture was stirred at room temperature for 2 days, and then concentrated under reduced pressure. Diethyl ether (5 mL) was added and filtered through a syringe filter (DISMIC-13HP manufactured by Advantec). The filtrate was concentrated to obtain hafnium complex 11. Yield 32.8 mg. Yield 78%. ¹ H-NMR (500 MHz, C ₆ D ₆ ) δ = 7.88 (d, J = 2.3 Hz, 2H), 7.66 (d, J = 2.3 Hz, 2H), 7.33-7. 31 (m, 1H), 7.20-6.98 (m, 6H), 6.68 (d, J = 4.4 Hz, 2H), 1.80 (s, 18H), 1.32 (s, 18H).

8). Synthesis of tin complex 12: Ligand precursor 6 (31 mg, 0.050 mmol) and tetrahydrofuran (0.5 mL) were placed in a glass vial under an argon atmosphere, and sodium hydride (9 mg, 0.36 mmol) was added. Then, it stirred at room temperature for 1 hour. The resulting reaction solution was filtered through a syringe filter (DISMIC-13HP from Advantec), washed with THF (2.5 mL), and the filtrates were transferred to another Schlenk reaction tube (20 mL). While stirring at room temperature, tin (IV) tetrachloride (6.5 × 10 ⁻³ mL, 0.056 mmol) was slowly added, and the mixture was stirred at room temperature for 3 hours and then concentrated under reduced pressure. Diethyl ether (5 mL) was added and filtered through a syringe filter (DISMIC-13HP manufactured by Advantec). The filtrate was concentrated to obtain tin complex 12 quantitatively. Yield 51.0 mg. ¹ H-NMR (500 MHz, C ₆ D ₆ ) δ = 7.70 (d, J = 2.3 Hz, 2H), 7.68 (d, J = 2.3 Hz, 2H), 7.30-6. 98 (m, 5H), 6.94 (d, J = 4.6 Hz, 2H), 6.64 (d, J = 4.6 Hz, 2H), 1.89 (s, 18H), 1.31 ( s, 18H).

9. Synthesis of germanium complex 13: Under an argon atmosphere, ligand precursor 6 (31 mg, 0.050 mmol) and tetrahydrofuran (0.5 mL) were placed in a glass vial, and sodium hydride (8 mg, 0.34 mmol) was added. Thereafter, the mixture was stirred at room temperature for 17 hours. The resulting reaction solution was filtered through a syringe filter (DISMIC-13HP from Advantec), washed with THF (2.5 mL), and the filtrates were transferred to another Schlenk reaction tube (20 mL). While stirring at room temperature, germanium (IV) tetrachloride (6.5 × 10 ⁻³ mL, 0.057 mmol) was slowly added, stirred at room temperature for 2 hours, and concentrated under reduced pressure. Diethyl ether (5 mL) was added and filtered through a syringe filter (DISMIC-13HP manufactured by Advantec). The filtrate was concentrated to obtain germanium complex 13 quantitatively. Yield 38.0 mg. ¹ H-NMR (500 MHz, C ₆ D ₆ ) δ = 7.67 (d, J = 2.5 Hz, 2H), 7.56 (d, J = 2.5 Hz, 2H), 7.21-6. 99 (m, 5H), 6.71 (d, J = 4.6 Hz, 2H), 6.57 (d, J = 4.6 Hz, 2H), 1.80 (s, 18H), 1.29 ( s, 18H).

10. Alternating copolymerization of propylene oxide and carbon dioxide (Examples 10-15)
In a 50 mL pressure-resistant reaction vessel made of stainless steel under an argon atmosphere, the complex (7.1 × 10 ⁻³ mmol) and bis (triphenylphosphoranylidene) ammonium chloride (PPNCl) (4 mg, 7.1 × 10) shown in Table 4 were placed. ^-3 mmol), propylene oxide (1.0 mL, 14 mmol) was added, and then carbon dioxide (2.0 MPa) was injected. The mixture was stirred at the temperature shown in Table 4 for 12 hours to remove carbon dioxide. The resulting polymerization solution was dissolved in deuterated chloroform, and phenanthrene was added as an internal standard. After uniformly dissolving, a small amount is extracted, and from ¹ H-NMR spectrum, the amount of propylene oxide incorporated into the copolymer per unit time and per unit amount of metal [TOF, unit is mol・ (Mol Metal) ⁻¹ · h ⁻¹ ], ratio of copolymer (PPC) to cyclic propylene carbonate (PC) (PPC / PC), carbonate linkage in the copolymer (carbonate linkage,%) and ether The bonding ratio (m: n) was estimated. The remaining polymerization product and NMR sample were combined and transferred to a glass flask using methylene chloride. 0.1 mL of a mixed solution of methanol and 1M hydrochloric acid (mixing ratio is methanol / 1M hydrochloric acid = 95/5) was added and stirred for 1 minute, followed by concentration. The resulting residue was dissolved in a small amount of methylene chloride and poured into methanol to precipitate a polymer. The number average molecular weight (M _n , g · mol ⁻¹ ) and molecular weight distribution (M _w / M _n ) of the obtained copolymer were estimated by high performance liquid chromatography.

11. Alternating copolymerization of cyclohexene oxide and carbon dioxide (Examples 16-21)
In an argon atmosphere, in a stainless steel 50 mL pressure resistant reaction vessel, the complex shown in Table 5 (10 × 10 ⁻³ mmol) and bis (triphenylphosphoranylidene) ammonium chloride (PPNCl) (6 mg, 10 × 10 ⁻³ mmol) After adding cyclohexene oxide (2.0 mL, 20 mmol), carbon dioxide (2.0 MPa) was injected under pressure. The mixture was stirred at the temperature shown in Table 5 for 12 hours to remove carbon dioxide. The resulting polymerization solution was dissolved in deuterated chloroform, and phenanthrene was added as an internal standard. After dissolving uniformly, a small amount was extracted and a ¹ H-NMR spectrum was measured. The remaining polymerization product and NMR sample were combined and transferred to a glass flask using methylene chloride. 0.1 mL of a mixed solution of methanol and 1M hydrochloric acid (mixing ratio is methanol / 1M hydrochloric acid = 95/5) was added and stirred for 1 minute, followed by concentration. The ratio (PCHC / CHC) of copolymer (PCHC) and cyclic cyclohexene carbonate (CHC) was estimated from the IR spectrum, and from this result and the result of the NMR spectrum measurement, per unit time and per unit amount of metal per metal. The amount of cyclohexene oxide incorporated in the copolymer [TOF, the unit is mol · (mol Metal) ⁻¹ · h ⁻¹ ], the carbonate linkage (%) and the ether linkage of the carbonate linkage in the copolymer. The ratio (m: n) was estimated. The resulting residue was dissolved in a small amount of methylene chloride and poured into methanol to precipitate a polymer. The number average molecular weight (M _n , g · mol ⁻¹ ) and molecular weight distribution (M _w / M _n ) of the obtained copolymer were estimated by high performance liquid chromatography.

  The present invention is very useful for industrial production of polycarbonate using carbon dioxide as a carbon source. In addition, the aliphatic polycarbonate obtained by the present invention can be used in various applications, for example, as an optical material, a thermally decomposable material, a medical material, a biodegradable resin, and the like.

Claims (10)

  A divalent or trivalent tetradentate ligand tetradentately coordinated to the tetravalent metal by one or more types of heteroatoms selected from the group consisting of a tetravalent metal and nitrogen, oxygen, sulfur and phosphorus A method for producing a polycarbonate, comprising copolymerizing an epoxide compound and carbon dioxide in the presence of a metal complex comprising: The metal complex has the formula (I):

Or formula (IV):

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or Selected from the group consisting of an unsubstituted aryloxycarbonyl group, a substituted or unsubstituted aralkyloxycarbonyl group, and a substituted or unsubstituted amino group, or two R ² and / or on adjacent carbon atoms two R ³ on adjacent carbon atoms, also form a substituted or unsubstituted aliphatic or aromatic ring bonded to each other Ku; R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, Selected from the group consisting of a substituted or unsubstituted heteroaryl group, a halogeno group, a nitro group, a substituted or unsubstituted amino group, and a cyano group, or two R ⁵ on adjacent carbon atoms are They may combine to form a substituted or unsubstituted aliphatic or aromatic ring; M is selected from the group consisting of titanium, zirconium, hafnium, ruthenium, osmium, platinum, tin, lead, germanium and cerium. X and Z are each independently F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate, aromatic carbon The anionic ligand selected from the group consisting of boxylates, alkoxides, and aryloxides). The metal complex has the formula (III):

Or the formula (V):

Wherein M is a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, tin, germanium and ruthenium; X and Z are each independently F ⁻ , Cl ⁻ , Br ⁻ , The anionic ligand selected from the group consisting of I ⁻ , N ₃ ⁻ , aliphatic carboxylate, aromatic carboxylate, alkoxide, and aryloxide. . [R ⁶ ₄ N] ⁺ , [R ⁶ ₄ P] ⁺ , [R ⁶ ₃ P = N = PR ⁶ ₃ ] ⁺ and formula (VI):

(In the formula, each R ⁶ is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; R ⁷ is 0 to 3 substituents on the carbon of the imidazolium ring, each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or substituted or unsubstituted And a cation containing phosphorus and / or nitrogen selected from the group consisting of F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate An epoxide compound and carbon dioxide are copolymerized using a promoter comprising a salt with an anion selected from the group consisting of aromatic carboxylate, alkoxide, and aryloxide in combination with the metal complex. The method according to, characterized in Rukoto any one of claims 1 to 3. A divalent or trivalent tetradentate ligand tetradentately coordinated to the tetravalent metal by one or more types of heteroatoms selected from the group consisting of a tetravalent metal and nitrogen, oxygen, sulfur and phosphorus A metal complex containing
[R ⁶ ₄ N] ⁺ , [R ⁶ ₄ P] ⁺ , [R ⁶ ₃ P = N = PR ⁶ ₃ ] ⁺ and formula (VI):

(In the formula, each R ⁶ is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; R ⁷ is 0 to 3 substituents on the carbon of the imidazolium ring, each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or substituted or unsubstituted And a cation containing phosphorus and / or nitrogen selected from the group consisting of F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate A promoter comprising a salt with an anion selected from the group consisting of: an aromatic carboxylate, an alkoxide, and an aryloxide;
Including a catalyst system. The metal complex has the formula (I):

Or formula (IV):

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or Selected from the group consisting of an unsubstituted aryloxycarbonyl group, a substituted or unsubstituted aralkyloxycarbonyl group, and a substituted or unsubstituted amino group, or two R ² and / or on adjacent carbon atoms two R ³ on adjacent carbon atoms, also form a substituted or unsubstituted aliphatic or aromatic ring bonded to each other Ku; R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, Selected from the group consisting of a substituted or unsubstituted heteroaryl group, a halogeno group, a nitro group, a substituted or unsubstituted amino group, and a cyano group, or two R ⁵ on adjacent carbon atoms are They may combine to form a substituted or unsubstituted aliphatic or aromatic ring; M is selected from the group consisting of titanium, zirconium, hafnium, ruthenium, osmium, platinum, tin, lead, germanium and cerium. X and Z are each independently F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate, aromatic carbon 6. The catalyst system according to claim 5, wherein the catalyst system is an anionic ligand selected from the group consisting of a boxylate, an alkoxide, and an aryloxide. The metal complex has the formula (III):

Or the formula (V):

Wherein M is a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, tin, germanium and ruthenium; X and Z are each independently F ⁻ , Cl ⁻ , Br ⁻ , The anion ligand selected from the group consisting of I ⁻ , N ₃ ⁻ , aliphatic carboxylate, aromatic carboxylate, alkoxide, and aryloxide. system. Formula (I):

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or Selected from the group consisting of an unsubstituted aryloxycarbonyl group, a substituted or unsubstituted aralkyloxycarbonyl group, and a substituted or unsubstituted amino group, or two R ² and / or on adjacent carbon atoms two R ³ on adjacent carbon atoms, also form a substituted or unsubstituted aliphatic or aromatic ring bonded to each other Ku; M is titanium, zirconium, hafnium, ruthenium, osmium, platinum, tin, be a tetravalent metal selected lead, from the group consisting of germanium and cerium; Z ^{is, F -, Cl -, Br} -, I ^-, N ₃ ^-., aliphatic carboxylate, aromatic carboxylate, represented by alkoxide, and is an anionic ligand selected from the group consisting of aryloxides), a metal complex. Formula (II):

Wherein R ¹ and R ³ are each independently a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl Group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl Selected from the group consisting of an oxycarbonyl group, a substituted or unsubstituted aralkyloxycarbonyl group, and a substituted or unsubstituted amino group; M is titanium, zirconium, hafnium, ruthenium, osmium, platinum, tin, lead, germanium and A tetravalent metal selected from the group consisting of cerium; Z is F ⁻ , Cl ^−. , Br ⁻ , I ⁻ , N ₃ ⁻ , an anionic ligand selected from the group consisting of aliphatic carboxylates, aromatic carboxylates, alkoxides, and aryloxides. Metal complexes described in 1. Formula (III):

Wherein M is a tetravalent metal selected from the group consisting of titanium, zirconium, hafnium, tin, germanium and ruthenium; Z is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , The metal complex according to claim 9, which is an anionic ligand selected from the group consisting of an aliphatic carboxylate, an aromatic carboxylate, an alkoxide, and an aryloxide.