JP2009215529A - Method for producing polycarbonate resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polycarbonate resin, which utilizes carbon dioxide as a carbon source and therefore gives consideration of the utilization of resources and the protection of the environment. <P>SOLUTION: In the method for producing the polycarbonate resin, the alternating copolymerization of carbon dioxide and an epoxide is carried out in the presence of an optically active cobalt complex catalyst optionally using a nucleophilic agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a polycarbonate resin, and more particularly to a method for producing a polycarbonate resin in which carbon dioxide and epoxide are alternately copolymerized in the presence of an optically active cobalt complex catalyst, optionally using a nucleophile.

  In the field of manufacturing synthetic resins including polycarbonate resins, the use of carbon dioxide as a carbon source is an important issue from the viewpoint of resource utilization and environmental protection. Polycarbonate resin has excellent properties such as impact resistance, lightness, transparency, and heat resistance. Among them, aliphatic polycarbonate resin is biodegradable, and has a low environmental impact. It can be said that it is an important resin as a medical material because of its characteristics.

  Conventionally, a method for producing a polycarbonate resin by a copolymerization reaction of carbon dioxide and epoxide is known. And as a catalyst used for the copolymerization reaction of this carbon dioxide and an epoxide, it is mainly a zinc complex (nonpatent literature 1), an aluminum complex (nonpatent literature 2), a porphyrin complex (patent literature 1), a salen complex ( Non-Patent Document 3).

  Zinc complexes are difficult to handle because diethyl zinc, which is a raw material, easily ignites, and are expensive. Aluminum complexes require high temperature and pressure as reaction conditions. There is a problem of cost. The porphyrin complex has problems that it is relatively difficult to synthesize, and that when used as a catalyst, the complex is colored, so that the color remains in the product.

  From the viewpoints of resource utilization and environmental protection, it is urgent to realize industrialization of polycarbonate resin by copolymerization reaction of carbon dioxide and epoxide. Therefore, establishment of the manufacturing method of polycarbonate resin using the outstanding catalyst which solves the said problem is strongly desired.

JP 2006-241247 A G.-W. Coates et al., J. Am. Chem. Soc. 2002, 124, 14284-14285 W. Kuran, T. Listos, M. Abramczyk, and A. Dawidek, J. Macromol. Sci., Pure Appl. Chem., A35, 427-437 (1998) G.-W. Coates et al., Angew. Chem. Int. Ed. 2003, 42, 5484-5487

  The objective of this invention is providing the manufacturing method of the polycarbonate resin which solved the said subject in the manufacturing method of the conventional polycarbonate resin. Another object of the present invention is to provide a polycarbonate as a completely alternating copolymer that exhibits various unprecedented physical properties and contributes to the development of new applications.

  As a result of intensive studies to achieve the above object, the present inventors have determined that an epoxide represented by the general formula (1) is replaced with carbon dioxide and an optically active cobalt represented by the general formula (2) or the general formula (3). By reacting in the presence of the complex, it was found that a polycarbonate resin can be obtained in a high yield under mild conditions, and the present invention has been completed.

That is, the present invention
1. General formula (1):

(Wherein R ¹ and R ² may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group, or R ¹ and R ² are May be bonded to each other to form a substituted or unsubstituted ring)
The epoxide represented by carbon dioxide and general formula (2) or general formula (3):

(In the formula, R ³ and R ⁴ may be the same or different, and independently of each other, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted group; It may be an aromatic heterocyclic group, or two R ^{3 s} or two R ^{4 s} may be bonded to each other to form a substituted or unsubstituted ring, and R ⁵ , R ⁶ and R ⁷ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted aromatic heterocyclic group, An acyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aromatic oxycarbonyl group, or a substituted or unsubstituted aralkyloxycarbonyl group, and R ⁶ and R ⁷ are And may be bonded to each other to form a substituted or unsubstituted aliphatic ring, and X ⁻ in the general formula (3) represents an anion pair capable of forming a salt)
Including reaction with an optically active cobalt complex represented by the general formula (4):

(Wherein R ¹ and R ² are as described above)
A method for producing a polycarbonate resin represented by:

2. In the general formula (1), one of R ¹ and R ² is a hydrogen atom, and the other is a substituted or unsubstituted alkyl group. The production method according to

3. The epoxide represented by the general formula (1) is:

Selected from the group consisting of: The production method according to

4). In General Formula (2) and General Formula (3), R ³ and R ⁴ are a hydrogen atom or a substituted or unsubstituted aromatic group, or two R ^{3 s} or two R ^{4 s} are mutually ^{May be} bonded to form a substituted or unsubstituted ring, and R ⁵ , R ⁶ and R ⁷ may be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or non-substituted group; 1. A substituted aralkyloxycarbonyl group as described in 1 above. ~ 3. The production method according to any one of

5. In the general formula (3), X ⁻ is OBzF ₅ ⁻ , OBz ⁻ , NO ₃ ⁻ , OCOCF ₃ ⁻ , F ⁻ or I ⁻ . ~ 4. The production method according to any one of

6). The optically active cobalt complexes represented by the general formula (2) and the general formula (3) are as follows:

Selected from the group consisting of: ~ 5. The production method according to any one of

7). Using a nucleophile, the above 1. ~ 6. The production method according to any one of
8). General formula (1):

(Wherein R ¹ and R ² may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group, or R ¹ and R ² are May be bonded to each other to form a substituted or unsubstituted ring)
8. A polycarbonate obtained by alternately bonding epoxides and carbon dioxide represented by formula ( ¹⁾ , wherein the polycarbonate does not contain an ether bond component detectable by ¹ H-NMR analysis; The present invention relates to polyethylene carbonate obtained by alternately bonding ethylene oxide and carbon dioxide, and does not contain an ether bond component detectable by ¹ H-NMR analysis.

  According to the method of the present invention, a polycarbonate resin can be produced in a high yield by using carbon dioxide as a carbon source and using an inexpensive and easy-to-synthesize cobalt catalyst. In addition, since the activity and selectivity of the catalyst are high and the reaction conditions do not require high temperature and pressure, the production cost can be reduced. Furthermore, since the polycarbonate according to the present invention is a completely alternating copolymer, it exhibits various unprecedented physical properties and contributes to the development of new applications.

Hereinafter, the present invention will be described in detail.
General formula (1) used as a raw material:

R ¹ and R ² may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group, or R ¹ and R ² R ² may be bonded to each other to form a substituted or unsubstituted ring.

The alkyl group for R ¹ and R ² is preferably a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. N-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, iso-pentyl 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-nonyl group, n-decyl group and the like, and more preferably a methyl group. The alkyl group is substituted with one or more substituents selected from, for example, a hydroxy group, amino group, carboxyl group, sulfanyl group, cyano group, sulfo group, formyl group, halogen atom, aromatic group and the like. May be.

The substituted or unsubstituted aromatic group for R ¹ and R ² is preferably a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, such as a phenyl group, an indenyl group, a naphthyl group, a tetrahydronaphthyl group, and the like. A substituted or unsubstituted aromatic hydrocarbon group is mentioned, More preferably, it is a phenyl group. Examples of the aromatic group include aromatic groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, a phenyl group, and a naphthyl group. It may be substituted with one or more substituents selected from a group and the like.

R ¹ and R ² 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 ¹ and R ² are bonded to each other via — (CH ₂ ) ₄ —, a cyclohexane ring is formed. 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, phenyl group, naphthyl group, etc. It may be substituted with one or two or more substituents selected from the following aromatic groups.

  Specific examples of particularly preferable epoxides represented by the general formula (1) include those represented by the following formulas (1-1) to (1-4).

  The optically active cobalt complex used as the catalyst has the general formula (2):

It is represented by Here, R ³ and R ⁴ may be the same or different, and are independently of each other a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted aromatic group. It may be a group heterocyclic group.

The substituted or unsubstituted alkyl group for R ³ and R ⁴ is preferably a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. , Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and the like. The alkyl group is substituted with one or more substituents selected from, for example, a hydroxy group, amino group, carboxyl group, sulfanyl group, cyano group, sulfo group, formyl group, halogen atom, aromatic group and the like. May be.

The substituted or unsubstituted aromatic group for R ³ and R ⁴ is preferably a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, such as a substituted or unsubstituted aromatic group such as a phenyl group or a naphthyl group. A hydrocarbon group is mentioned. Examples of the aromatic group include aromatic groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, a phenyl group, and a naphthyl group. It may be substituted with one or more substituents selected from a group and the like.

The substituted or unsubstituted aromatic heterocyclic group for R ³ and R ⁴ is preferably a substituted or unsubstituted aromatic heterocyclic group having 5 to 10 carbon atoms, such as a furyl group, a thienyl group, a pyridyl group, pyrrolyl. And substituted or unsubstituted aromatic heterocyclic 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 aromatic heterocyclic group includes, for example, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups and other alkyl groups, phenyl groups, naphthyl groups, and the like. It may be substituted with one or more substituents selected from aromatic groups and the like.

Further, two R ^{3 s} or two R ^{4 s} may be bonded to each other to form a substituted or unsubstituted ring, preferably a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms. May be formed. For example, when R ³ and R ⁴ are bonded to each other via — (CH ₂ ) ₄ —, a cyclohexane ring is formed. 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, phenyl group, naphthyl group, etc. It may be substituted with one or two or more substituents selected from the following aromatic groups.

Further, R ⁵ , R ⁶ and R ⁷ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, substituted or unsubstituted An unsubstituted aromatic heterocyclic group, an acyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aromatic oxycarbonyl group, or a substituted or unsubstituted aralkyloxycarbonyl group.

The substituted or unsubstituted alkyl group for R ⁵ , R ⁶ and R ⁷ is preferably a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. And a linear or branched substituted or unsubstituted 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, and a tert-butyl group. . The alkyl group is substituted with one or more substituents selected from, for example, a hydroxy group, amino group, carboxyl group, sulfanyl group, cyano group, sulfo group, formyl group, halogen atom, aromatic group and the like. May be.

The substituted or unsubstituted alkenyl group for R ⁵ , R ⁶ and R ⁷ is preferably a linear or branched alkenyl group having 2 to 10 carbon atoms, more preferably a linear or branched group having 2 to 6 carbon atoms. Examples of the chain alkenyl group include a vinyl group and a 2-propenyl group. The alkenyl group is substituted with one or more substituents selected from, for example, a hydroxy group, amino group, carboxyl group, sulfanyl group, cyano group, sulfo group, formyl group, halogen atom, aromatic group and the like. May be.

The aromatic group for R ⁵ , R ⁶ and R ⁷ is preferably a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, for example, a substituted or unsubstituted aromatic hydrocarbon such as a phenyl group or a naphthyl group. Groups. Examples of the aromatic group include aromatic groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, a phenyl group, and a naphthyl group. It may be substituted with one or more substituents selected from a group and the like.

The substituted or unsubstituted aromatic heterocyclic group for R ⁵ , R ⁶ and R ⁷ is preferably a substituted or unsubstituted aromatic heterocyclic group having 5 to 10 carbon atoms, such as a furyl group, a thienyl group, a pyridyl group. A substituted or unsubstituted aromatic heterocyclic group such as a group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, pyrimidyl group, pyridazinyl group, pyralidinyl group, quinolyl group, isoquinolyl group, etc. Can be mentioned. The aromatic heterocyclic group is, for example, one or more substituents selected from an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, a halogen atom group, a nitro group, and a cyano group It may be substituted with a group.

As the acyl group of R ⁵ , R ⁶ and R ⁷ , an acyl group having 1 to 20 carbon atoms is preferable. For example, formyl group, acetyl group, trifluoroacetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, etc. Aliphatic acyl group, benzoyl group, 3,5-dimethylbenzoyl group, 2,4,6-trimethylbenzoyl group, 2,6-dimethoxybenzoyl group, 2,4,6-trimethoxybenzoyl group, 2,6- Examples thereof include aromatic acyl groups such as diisopropoxybenzoyl group, 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, and 9-anthrylcarbonyl group.

The substituted or unsubstituted alkoxycarbonyl group for R ⁵ , R ⁶ and R ⁷ is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, n-butoxy. Examples thereof include a carbonyl group, an n-octyloxycarbonyl group, a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, a cyclooctyloxycarbonyl group, an adamantyloxycarbonyl group, and a tert-butoxycarbonyl group. The alkoxycarbonyl group is substituted with one or more substituents selected from, for example, a hydroxy group, an amino group, a carboxyl group, a sulfanyl group, a cyano group, a sulfo group, a formyl group, a halogen atom, and an aromatic group. It may be.

The substituted or unsubstituted aromatic oxycarbonyl group for R ⁵ , R ⁶ and R ⁷ is preferably a substituted or unsubstituted aromatic oxycarbonyl group having 7 to 20 carbon atoms, and examples thereof include a phenoxycarbonyl group. The aromatic oxycarbonyl group is, for example, one or more substitutions selected from alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, halogen atom group, nitro group, cyano group and the like It may be substituted with a group.

The substituted or unsubstituted aralkyloxycarbonyl group for R ⁵ , R ⁶ and R ⁷ is preferably an aralkyloxycarbonyl group having 7 to 20 carbon atoms, and examples thereof include a benzyloxycarbonyl group and a phenethyloxycarbonyl group. The aralkyloxycarbonyl group is selected from, for example, hydroxy group, amino group, carboxyl group, sulfanyl group, cyano group, sulfo group, formyl group, halogen atom, aromatic group, alkoxyalkyleneoxy group, such as methoxyethyleneoxy group Optionally substituted with one or more substituents.

Furthermore, R ⁶ and R ⁷ may be bonded to each other to form a ring, and may preferably form a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms. For example, when R ⁶ and R ⁷ are bonded to each other via — (CH ₂ ) ₄ —, a cyclohexane ring is formed. 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, phenyl group, naphthyl group, etc. It may be substituted with one or two or more substituents selected from the following aromatic groups.

  Specific examples of particularly preferable optically active cobalt complexes represented by the general formula (2) include those represented by the following formulas (2-1) to (2-11).

  In the present invention, the general formula (3) obtained by deriving from the optically active cobalt complex represented by the general formula (2):

Is also effective as an optically active cobalt complex used in the method of the present invention, wherein R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are defined with respect to the general formula (2). And X ⁻ represents an anion pair capable of forming a salt.

X ⁻ in the general formula (3) includes I ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , BF ₄ ⁻ , OCOCF ₃ ⁻ , NO ₂ ⁻ and NO. ₃ ⁻ , CH ₃ CO ₂ ⁻ , OBz ⁻ , OBzF ₅ ⁻ , OBz (3 _, 5CF ₃ ) ⁻ , OBz (3 _, 5Cl) ⁻ , OBz (4Me ₂ N) ⁻ , OBz (4tBu) ⁻ , F ⁻ , Cl ⁻ , Br ⁻ , OH ⁻ , PF ₆ ⁻ , BPh ₄ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , OTf ⁻ , OTs ^{− and the} like can be mentioned, and OBzF ₅ ⁻ , OBz ⁻ , NO ₃ ⁻ , OCOCF ₃ are preferable. ^-, or I ^- it is.

  Specific examples of particularly preferable optically active cobalt complexes represented by the general formula (3) include those represented by the following formulas (3-1) to (3-14).

  The polycarbonate resin produced in the method of the present invention has the general formula (4):

Where R ¹ and R ² are as described above.

  The molecular weight of the polycarbonate resin represented by the general formula (4) is preferably about 1,000 to 100,000, more preferably about 2,000 to 50,000, and particularly preferably about 2,500 to 40,000. Range.

  Specific examples of particularly preferable polycarbonate resins represented by the general formula (4) include those represented by the following formulas (4-1) to (4-4).

Nucleophiles can be used in the method of the present invention.
The nucleophile works as a polymerization initiator, but when no nucleophile is used, it is considered that a trace amount of water works as the polymerization initiator.

Nucleophiles include bis (triphenylphosphoranylidene) ammonium chloride (PPNCl), piperidine, bis (triphenylphosphoranylidene) ammonium fluoride (PPNF), bis (triphenylphosphoranylidene) ammonium penta Fluorobenzoate (PPNOBzF ₅ ), nBu ₄ NCl, nBu ₄ NBr, nBu ₄ NBr ₃ , nBu ₄ NI, nBu ₄ NOAc, Ph ₃ P, etc. are mentioned, preferably PPNCl, PPNF, PPNOBzF ₅ or nBu ₄ NCl More preferably, it is PPNF.

Although there is no restriction | limiting in particular in the usage-amount of the carbon dioxide used in this invention, Usually, it reacts on carbon dioxide atmosphere or a carbon dioxide pressurization condition. Among these, a preferable carbon dioxide pressure is in the range of 0.1 MPa to 10 MPa, more preferably 0.1 MPa to 2 MPa. In addition, the reaction can be performed under a mixed gas of an inert gas and carbon dioxide that does not significantly affect the reaction such as nitrogen or argon.
The reaction temperature is usually preferably -40 ° C to 50 ° C, and more preferably 0 ° C to 30 ° C.
Although reaction time changes with reaction conditions, it is 1 to 100 hours normally.

  Moreover, in this invention, a solvent can be used as needed. The solvent used is not particularly limited as long as it does not react with the epoxide, carbon dioxide, optically active cobalt complex, or nucleophile used. For example, hydrocarbons, ethers, esters, ketones, halogenated compounds. And hydrocarbons. Specifically, hexane, benzene, toluene, xylene, cyclohexane, dibutyl ether, tetrahydrofuran, 1,4-dioxane, methyl acetate, ethyl acetate, propyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methylene chloride, chloroform, dichloroethane , Trichloroethane, chlorobenzene and the like, preferably chloroform. These may be used alone or in combination of two or more. As a usage-amount of a solvent, it can add in 0.5-100, preferably 1-50 in mass ratio with respect to the epoxide which is a raw material.

The polycarbonate obtained by the method of the present invention is considered to contribute to the development of new applications by exhibiting unprecedented high physical properties because it is a completely alternating copolymer. In particular, the polycarbonate according to the present invention is thermally decomposed at a relatively low temperature and has almost no decomposition residue, as shown in the examples described later (FIG. 3). Thus, the polycarbonate by this invention excellent in heat decomposability is useful as binder resin for manufacturing the various molded object which consists of a ceramic and glass manufactured through a degreasing | defatting and baking process, for example. Furthermore, the polycarbonate according to the present invention is higher in quality than conventional polycarbonates in terms of various properties such as impact resistance, lightness, transparency, heat resistance, biodegradability, etc. It can be advantageously applied in various applications.
Examples are shown below, but the present invention is not limited to these (herein, the ketoiminato cobalt complex is indicated by the numbers in the above specific examples).

(Alternate copolymerization of propylene oxide and CO ₂ )
Example 1
In a stainless steel pressure vessel, 0.0143 mmol of ketoiminatocobalt pentafluorobenzoate complex (3-1) and 0.0143 mmol of bis (triphenylphosphoranylidene) ammonium fluoride (PPNF) were added, and 28.6 mmol of propylene oxide was added. Thereafter, carbon dioxide was injected under pressure to adjust the total pressure to 2.0 MPa. After reacting at room temperature for 48 hours, carbon dioxide was removed, and the reaction mixture was analyzed by ¹ H-NMR. ¹ H-NMR analysis was performed at a temperature of 22 ° C. using deuterated chloroform as a solvent and tetramethylsilane as an internal standard. Further, JOEL-EX270 and GX-400 manufactured by JEOL Ltd. were used for the ¹ H-NMR measuring apparatus.

In the obtained reaction mixture, 99% or more of polycarbonate in which carbon dioxide and propylene oxide were alternately reacted was present, and almost no cyclic carbonate was produced in which carbon dioxide and propylene oxide were reacted one molecule at a time. . Furthermore, by ¹ H-NMR, the proportion of carbonate bonds contained in the polycarbonate chain was 99% or more, that is, the product was a complete alternating copolymer. The yield of the obtained polycarbonate was 72%, and the head-to-tail bond selectivity was 92% by ¹³ C-NMR. When the obtained polycarbonate was analyzed by GPC, the number average molecular weight Mn was 16800, and the molecular weight distribution Mw / Mn was 1.2 (standard polystyrene standard, THF).

Example 2
The reaction was conducted in the same manner as in Example 1 except that PPNF was changed to bis (triphenylphosphoranylidene) ammonium chloride (PPNCl). The reaction mixture obtained at this time contained about 38% cyclic carbonate. Yield was 54%, head-to-tail bond selectivity was 92%, Mn was 15700, and Mw / Mn was 1.2 (standard polystyrene standard, THF).

Example 3
The reaction was conducted in the same manner as in Example 1 except that PPNF was changed to bis (triphenylphosphoranylidene) ammonium pentafluorobenzoate (PPNOBzF ₅ ). The reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. Yield was 64%, head-to-tail bond selectivity was 92%, Mn was 25400, and Mw / Mn was 1.7 (standard polystyrene standard, THF).

Example 4
The reaction was conducted in the same manner as in Example 1 except that PPNF was changed to tetra-n-butylammonium chloride. The reaction mixture obtained at this time contained about 4% cyclic carbonate. Yield was 43%, head-to-tail bond selectivity was 91%, Mn was 17900, and Mw / Mn was 1.0 (standard polystyrene standard, THF).

Example 5
The reaction was conducted in the same manner as in Example 1 except that PPNF was changed to triphenylphosphine. The reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. Yield was 10%, head-to-tail bond selectivity was 85%, Mn was 4400, and Mw / Mn was 1.1 (standard polystyrene standard, THF).

(Examination of nucleophiles)
Examples 6-17
In Example 1 above, the reaction was carried out in the same manner unless otherwise specified except that the nucleophile was changed. The results are shown in the following table (standard polystyrene standard, chloroform).

Example 18
The reaction was carried out in the same manner as in Example 1 except that the ketoiminato cobalt pentafluorobenzoate complex was changed to the ketoiminato cobalt benzoate complex (3-2). The reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. Yield was 85%, head-to-tail bond selectivity was 91%, Mn was 26400, and Mw / Mn was 1.7 (standard polystyrene standard, THF).

Example 19
The reaction was conducted in the same manner as in Example 1 except that the ketoiminato cobalt pentafluorobenzoate complex was changed to the ketoiminato cobalt nitrate complex (3-3). The reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. Yield was 81%, head-to-tail bond selectivity was 91%, Mn was 16900, and Mw / Mn was 1.2 (standard polystyrene standard, THF).

Example 20
The reaction was carried out in the same manner as in Example 1 except that the ketiminato cobalt pentafluorobenzoate complex was changed to the ketiminato cobalt trifluoroacetate complex (3-4). The reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. The yield was 82%, the head-to-tail bond selectivity was 91%, Mn was 26500, and Mw / Mn was 1.7 (standard polystyrene standard, THF).

Example 21
The reaction was conducted in the same manner as in Example 1 except that the ketoiminatocobalt pentafluorobenzoate complex was changed to the ketoiminatocobalt iodide complex (3-5). The reaction mixture obtained at this time contained about 36% cyclic carbonate. Yield was 50%, head-to-tail bond selectivity was 77%, Mn was 4200, and Mw / Mn was 1.0 (standard polystyrene standard, THF).

Example 22
The reaction was conducted in the same manner as in Example 1 except that the ketoiminatocobalt pentafluorobenzoate complex was changed to the ketoiminatocobalt iodide complex (3-6). The reaction mixture obtained at this time contained about 43% cyclic carbonate. Yield was 41%, head-to-tail bond selectivity was 76%, Mn was 8200, and Mw / Mn was 1.4 (standard polystyrene standard, chloroform).

Example 23
The reaction was carried out in the same manner as in Example 1 except that the ketiminato cobalt pentafluorobenzoate complex was changed to the ketiminato cobalt (II) complex (2-1). The reaction mixture obtained at this time contained about 3% cyclic carbonate. Yield was 57%, head-to-tail bond selectivity was 92%, Mn was 20700, and Mw / Mn was 1.4 (standard polystyrene standard, THF).

Examination of ligand in complex (Examples 24-28)
In Example 1 above, the reaction was carried out in the same manner unless otherwise specified except that the complex was changed and PPNF was changed to PPNCl. The results are shown in the following table (standard polystyrene standard, chloroform).

(Examination of anion pairs in complexes)
Examples 29-41
In Example 1 above, the reaction was carried out in the same manner unless otherwise specified except that the anion pair of the ketiminato cobalt pentafluorobenzoate complex (3-1) was changed and PPNF was changed to PPNCl. The results are shown in the following table (standard polystyrene standard, chloroform).

Example 42
The reaction was performed in the same manner as in Example 1 except that the solvent-free place was changed to 2 mL of tetrahydrofuran solvent. The reaction mixture obtained at this time contained about 7% cyclic carbonate. Yield was 52%, head-to-tail bond selectivity was 88%, Mn was 13700, and Mw / Mn was 1.2 (standard polystyrene standard, THF).

Example 43
The reaction was conducted in the same manner as in Example 1 except that the solvent-free place was changed to 2 mL of methylene chloride solvent. The reaction mixture obtained at this time contained about 4% cyclic carbonate. Yield was 28%, head-to-tail bond selectivity was 89%, Mn was 9200, and Mw / Mn was 1.5 (standard polystyrene standard, THF).

Example 44
The reaction was conducted in the same manner as in Example 1 except that the solvent-free place was changed to 2 mL of chloroform solvent. The reaction mixture obtained at this time contained about 6% cyclic carbonate. Yield was 86%, head-to-tail bond selectivity was 82%, Mn was 12300, and Mw / Mn was 1.3 (standard polystyrene standard, THF).

Example 45
In Example 1, the reaction was performed in the same manner except that the reaction time was changed to 5 hours. The reaction mixture obtained at this time contained about 10% cyclic carbonate. Yield was 6%, head-to-tail bond selectivity was 91%, Mn was 4461, and Mw / Mn was 1.2 (standard polystyrene standard, THF).

Example 46
In Example 1 above, the reaction was performed in the same manner except that the reaction time was changed to 10 hours. The reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. Yield was 29%, head-to-tail bond selectivity was 91%, Mn was 15600, and Mw / Mn was 1.1 (standard polystyrene standard, THF).

Example 47
In Example 1 above, the reaction was carried out in the same manner except that the reaction time was changed to 15 hours. The reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. Yield was 34%, head-to-tail bond selectivity was 91%, Mn was 17300, and Mw / Mn was 1.0 (standard polystyrene standard, THF).

Example 48
In Example 1, the reaction was performed in the same manner except that the reaction time was changed to 24 hours. The reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. Yield was 56%, head-to-tail bond selectivity was 93%, Mn was 17400, and Mw / Mn was 1.0 (standard polystyrene standard, THF).

Example 49
In Example 1, the reaction was performed in the same manner except that the reaction time was changed to 72 hours. The reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. The yield was 69%, the head-to-tail bond selectivity was 92%, Mn was 33500, and Mw / Mn was 1.7 (standard polystyrene standard, THF).

Example 50
In Example 1 above, the reaction was carried out in the same manner except that the pressure vessel was previously dried under reduced pressure. The reaction mixture obtained at this time was polycarbonate with a selectivity of 99% or more. Yield was 83%, head-to-tail bond selectivity was 93%, Mn was 31000, and Mw / Mn was 1.6 (standard polystyrene standard, THF).

Example 51
In Example 10, the reaction was performed in the same manner except that the pressure vessel was previously dried under reduced pressure. The reaction mixture obtained at this time contained about 2% cyclic carbonate. Yield was 69%, head-to-tail bond selectivity was 92%, Mn was 17200, and Mw / Mn was 1.0 (standard polystyrene standard, THF).

Comparative Example 1
In Example 1 above, the reaction was conducted in the same manner except that the ketoiminato cobalt pentafluorobenzoate complex was not used, but the reaction did not proceed at all.

(Alternate copolymerization of cyclohexene oxide and CO ₂ )
Example 52
A stainless steel pressure vessel was charged with 0.0143 mmol of ketoiminatocobalt pentafluorobenzoate complex (3-1) and 0.0143 mmol of bis (triphenylphosphoranylidene) ammonium fluoride (PPNF), and 14.8 mmol of cyclohexene oxide was added. Thereafter, carbon dioxide was injected under pressure to adjust the total pressure to 2.0 MPa. After reacting at 30 ° C. for 48 hours, carbon dioxide was removed, and the reaction mixture was analyzed by ¹ H-NMR.

In the obtained reaction mixture, 99% or more of polycarbonate in which carbon dioxide and cyclohexene oxide were alternately reacted was present, and almost no cyclic carbonate was produced in which carbon dioxide and cyclohexene oxide were reacted one molecule at a time. . Furthermore, by ¹ H-NMR, the proportion of carbonate bonds contained in the polycarbonate chain was 99% or more, that is, the product was a complete alternating copolymer. The yield of the obtained polycarbonate was 58%. Further, when the obtained polycarbonate was analyzed by GPC, the number average molecular weight Mn was 6000, and the molecular weight distribution Mw / Mn was 1.4 (standard polystyrene standard, THF).

Example 53
The reaction was conducted in the same manner as in Example 52 except that PPNF was changed to bis (triphenylphosphoranylidene) ammonium chloride (PPNCl) and the reaction time was changed from 48 hours to 65 hours. The yield was 57%, Mn was 5100, and the molecular weight distribution Mw / Mn was 1.1 (standard polystyrene standard, THF).

Example 54
In Example 52, the reaction was performed in the same manner except that 0.5 mL of toluene was added as a solvent. The yield was 69%, Mn was 6000, and the molecular weight distribution Mw / Mn was 1.1 (standard polystyrene standard, THF).

Example 55
The reaction was carried out in the same manner as in Example 52 except that the ketiminato cobalt pentafluorobenzoate complex (3-1) was changed to the ketiminato cobalt iodide complex (3-5). The yield was 29%, Mn was 4500, and the molecular weight distribution Mw / Mn was 1.1 (standard polystyrene standard, THF).

Example 56
In Example 52, the reaction was performed in the same manner except that the ketiminato cobalt pentafluorobenzoate complex (3-1) was changed to ketiminato cobalt iodide complex (3-5), and PPNF was changed to PPNCl. . The yield was 5%, Mn was 1900, and the molecular weight distribution Mw / Mn was 1.1 (standard polystyrene standard, THF).

Example 57
In the above Example 52, the ketiminatocobalt pentafluorobenzoate complex (3-1) was changed to the ketiminatocobalt iodide complex (3-5), PPNF was changed to PPNCl, and 0.5 mL of toluene was further used as a solvent. The reaction was performed in the same manner except that it was added. The yield was 70%, Mn was 4300, and the molecular weight distribution Mw / Mn was 1.1 (standard polystyrene standard, THF).

Example 58
In Example 52, the reaction was carried out in the same manner except that the ketiminato cobalt pentafluorobenzoate complex (3-1) was changed to the ketiminato cobalt iodide complex (3-5), and 0.5 mL of toluene was added as a solvent. Went. The yield was 39%, Mn was 1500, and the molecular weight distribution Mw / Mn was 1.2 (standard polystyrene standard, THF).

  The results of Examples 52-58 are summarized in the table below.

(Alternate copolymerization of ethylene oxide and CO ₂ )
Example 59
An autoclave with an internal volume of 50 mL was charged with 5.8 mg (10 μmol) of ketoiminatocobalt iodide complex (3-5), 5.4 mg (10 μmol) of PPNF, 1.0 mL of methylene chloride, 1.56 g (35 mmol) of ethylene oxide, and carbon dioxide. It was charged (2.0 MPa) and reacted at 25 ° C. for 48 hours. Thereafter, the pressure was released, and diluted hydrochloric acid and methanol were added to stop the reaction. The contents were washed with dilute hydrochloric acid and poured into methanol to obtain a white precipitate. This was filtered and dried under reduced pressure to obtain 1.94 g of polyethylene carbonate. When this polycarbonate was analyzed by GPC (polystyrene standard), the number average molecular weight Mn was 22000, and Mw / Mn was 1.16. Moreover, from the analysis result by < ¹ > H-NMR, ratio of polyethylene carbonate and ethylene carbonate (cyclic carbonate) was 100: 0. The catalytic activity was 173 g / g catalyst (total amount of cobalt complex and PPNF).

Example 60
An autoclave with an internal volume of 50 mL was charged with 5.8 mg (10 μmol) of ketoiminatocobalt iodide complex (3-5), 5.7 mg (10 μmol) of PPNCl, 1.0 mL of methylene chloride, 1.50 g (34 mmol) of ethylene oxide, and carbon dioxide. It was charged (2.0 MPa) and reacted at 25 ° C. for 48 hours. Thereafter, the pressure was released, and diluted hydrochloric acid and methanol were added to stop the reaction. The contents were washed with dilute hydrochloric acid and poured into methanol to obtain a white precipitate. This was filtered and dried under reduced pressure to obtain 0.86 g of polyethylene carbonate. When this polycarbonate was analyzed by GPC (polystyrene standard), the number average molecular weight Mn was 8700, and Mw / Mn was 1.20. From the analysis result by ¹ H-NMR, the ratio of polyethylene carbonate to ethylene carbonate (cyclic carbonate) was 48:52. The catalytic activity was 74 g / g catalyst (total amount of cobalt complex and PPNCl).

Example 61
An autoclave having an internal volume of 50 mL was charged with 5.4 mg (10 μmol) of ketoiminatocobalt tetrafluoroborate complex (3-13), 5.7 mg (10 μmol) of PPNCl, 1.0 mL of methylene chloride, and 1.16 g (26 mmol) of ethylene oxide. (2.0 MPa) and reacted at 25 ° C. for 48 hours. Thereafter, the pressure was released, and diluted hydrochloric acid and methanol were added to stop the reaction. The contents were washed with dilute hydrochloric acid and poured into methanol to obtain a white precipitate. This was filtered and dried under reduced pressure to obtain 0.08 g of polyethylene carbonate. When this polycarbonate was analyzed by GPC (polystyrene standard), the number average molecular weight Mn was 4600, and Mw / Mn was 1.24. Moreover, from the analysis result by < ¹ > H-NMR, ratio of polyethylene carbonate and ethylene carbonate (cyclic carbonate) was 75:25. The catalytic activity was 7 g / g catalyst (total amount of cobalt complex and PPNCl).

Example 62
An autoclave having an internal volume of 50 mL was charged with 4.7 mg (10 μmol) of ketoiminato cobalt fluoride complex (3-14), 5.7 mg (10 μmol) of PPNCl, 1.0 mL of methylene chloride, 1.02 g (23 mmol) of ethylene oxide, and carbon dioxide. It was charged (2.0 MPa) and reacted at 25 ° C. for 48 hours. Thereafter, the pressure was released, and diluted hydrochloric acid and methanol were added to stop the reaction. The contents were washed with dilute hydrochloric acid and poured into methanol to obtain a white precipitate. This was filtered and dried under reduced pressure to obtain 1.04 g of polyethylene carbonate. When this polycarbonate was analyzed by GPC (polystyrene standard), the number average molecular weight Mn was 15000 and Mw / Mn was 1.13. Moreover, from the analysis result by < ¹ > H-NMR, ratio of polyethylene carbonate and ethylene carbonate (cyclic carbonate) was 100: 0. The catalytic activity was 100 g / g catalyst (total amount of cobalt complex and PPNCl).

Example 63
An autoclave with an internal volume of 50 mL was charged with 5.8 mg (10 μmol) of ketoiminatocobalt iodide complex (3-5), 5.4 mg (10 μmol) of PPNF, 1.0 mL of methylene chloride, 10.37 g (250 mmol) of ethylene oxide, and carbon dioxide. It was charged (2.0 MPa) and reacted at 25 ° C. for 48 hours. Thereafter, the pressure was released, and diluted hydrochloric acid and methanol were added to stop the reaction. The contents were washed with dilute hydrochloric acid and poured into methanol to obtain a white precipitate. This was filtered and dried under reduced pressure to obtain 2.45 g of polyethylene carbonate. When this polycarbonate was analyzed by GPC (polystyrene standard), the number average molecular weight Mn was 63000, and Mw / Mn was 1.17. Moreover, from the analysis result by < ¹ > H-NMR, ratio of polyethylene carbonate and ethylene carbonate (cyclic carbonate) was 100: 0. The catalytic activity was 219 g / g catalyst (total amount of cobalt complex and PPNF). The results of ¹ H-NMR analysis, DSC analysis and TGA analysis of the obtained polyethylene carbonate are shown in FIG. 1, FIG. 2 and FIG. 3, respectively.

Example 64
An autoclave with an internal volume of 50 mL was charged with 5.8 mg (10 μmol) of ketoiminatocobalt iodide complex (3-5), 5.4 mg (10 μmol) of PPNF, 1.0 mL of methylene chloride, 9.97 g (230 mmol) of ethylene oxide, and carbon dioxide. It was charged (2.0 MPa) and reacted at 40 ° C. for 48 hours. Thereafter, the pressure was released, and diluted hydrochloric acid and methanol were added to stop the reaction. The contents were washed with dilute hydrochloric acid and poured into methanol to obtain a white precipitate. This was filtered and dried under reduced pressure to obtain 3.45 g of polyethylene carbonate. When this polycarbonate was analyzed by GPC (polystyrene standard), the number average molecular weight Mn was 38000, and Mw / Mn was 1.41. Moreover, from the analysis result by ¹ H-NMR, the ratio of polyethylene carbonate and ethylene carbonate (cyclic carbonate) was 70:30. The catalytic activity was 338 g / g catalyst (total amount of cobalt complex and PPNF).

Comparative Example 2
The results of ¹ H-NMR analysis, DSC analysis, and TGA analysis of polyethylene carbonate (trade name: QPAC25) obtained from Empor are shown in FIGS. 4, 5, and 6, respectively.

The polyethylene carbonate obtained in Example 63 does not substantially contain a peak derived from an ether bond (around 3.6 ppm) in ¹ H-NMR analysis (FIG. 1). In FIG. 1, a peak (1% or less) that is slightly visible around 3.7 ppm is a peak derived from the proton of the terminal methylene group of polyethylene carbonate. Therefore, it can be said that this polyethylene carbonate is a completely alternating copolymer in which ethylene oxide and carbon dioxide are alternately polymerized one by one (even if an ether bond is present, the amount is below the detection limit of ¹ H-NMR analysis). Is). In contrast, commercially available polyethylene carbonate “QPAC25” has a peak derived from an ether bond (near 3.6 ppm) in addition to a peak derived from a terminal proton (near 3.7 ppm) in ¹ H-NMR analysis. About 5% is contained (FIG. 4). That is, this polyethylene carbonate includes a portion where ethylene oxides are bonded to each other.

  The polyethylene carbonate obtained in Example 63 had a glass transition temperature Tg of 17.5 ° C. in DSC analysis (FIG. 2). On the other hand, the commercially available polyethylene carbonate “QPAC25” had a glass transition temperature Tg of 15.7 ° C. in DSC analysis (FIG. 5). In addition, the polyethylene carbonate obtained in Example 63 was substantially completely decomposed at around 250 ° C. in the TGA analysis (FIG. 3). On the other hand, it was shown that about 5% of the commercially available polyethylene carbonate “QPAC25” was not decomposed even when the temperature exceeded 300 ° C. in TGA analysis, and 350 ° C. or more was required for complete decomposition (FIG. 6). Thus, since the polyethylene carbonate by this invention is a complete alternating copolymer, it turns out that it has the thermal characteristic remarkably different from the polyethylene carbonate which exists conventionally.

  The method according to the present invention is useful for industrialization of polycarbonate resin production using carbon dioxide as a carbon source. Further, the polycarbonate according to the present invention is a completely alternating copolymer, and thus exhibits various unprecedented physical properties and contributes to the development of new applications.

2 is a graph showing ¹ H-NMR analysis results of polyethylene carbonate synthesized in Example 63. FIG. 6 is a graph showing DSC analysis results of the polyethylene carbonate synthesized in Example 63. FIG. 7 is a graph showing a TGA analysis result of polyethylene carbonate synthesized in Example 63. FIG. It is a graph which shows the < ¹ > H-NMR analysis result of commercially available polyethylene carbonate. It is a graph which shows the DSC analysis result of commercially available polyethylene carbonate. It is a graph which shows the TGA analysis result of commercially available polyethylene carbonate.

Claims (9)

General formula (1):

(Wherein R ¹ and R ² may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group, or R ¹ and R ² are May be bonded to each other to form a substituted or unsubstituted ring)
The epoxide represented by carbon dioxide and general formula (2) or general formula (3):

(In the formula, R ³ and R ⁴ may be the same or different, and independently of each other, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted group; It may be an aromatic heterocyclic group, or two R ^{3 s} or two R ^{4 s} may be bonded to each other to form a substituted or unsubstituted ring, and R ⁵ , R ⁶ and R ⁷ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted aromatic heterocyclic group, An acyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aromatic oxycarbonyl group, or a substituted or unsubstituted aralkyloxycarbonyl group, and R ⁶ and R ⁷ are And may be bonded to each other to form a substituted or unsubstituted aliphatic ring, and X ⁻ in the general formula (3) represents an anion pair capable of forming a salt)
Including the reaction in the presence of an optically active cobalt complex represented by the general formula (4):

(Wherein R ¹ and R ² are as described above)
The manufacturing method of polycarbonate resin represented by these. The production method according to claim 1, wherein in general formula (1), one of R ¹ and R ² is a hydrogen atom, and the other is a substituted or unsubstituted alkyl group. The epoxide represented by the general formula (1) is:

The manufacturing method of Claim 1 selected from the group consisting of. In General Formula (2) and General Formula (3), R ³ and R ⁴ are a hydrogen atom or a substituted or unsubstituted aromatic group, or two R ^{3 s} or two R ^{4 s} are mutually ^{May be} bonded to form a substituted or unsubstituted ring, and R ⁵ , R ⁶ and R ⁷ may be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or non-substituted group; The manufacturing method of any one of Claims 1-3 which is a substituted aralkyloxycarbonyl group. _5. The production method according to claim 1, wherein, in the general formula (3), X ⁻ is OBzF ₅ ⁻ , OBz ⁻ , NO ₃ ⁻ , OCOCF ₃ ⁻ , F ⁻ or I ⁻ . The optically active cobalt complexes represented by the general formula (2) and the general formula (3) are as follows:

The manufacturing method of any one of Claims 1-5 selected from the group which consists of.   The manufacturing method of any one of Claims 1-6 using a nucleophile. General formula (1):

(Wherein R ¹ and R ² may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group, or R ¹ and R ² are May be bonded to each other to form a substituted or unsubstituted ring)
A polycarbonate obtained by alternately bonding epoxides and carbon dioxide, which does not contain an ether bond component detectable by ¹ H-NMR analysis. Polyethylene carbonate obtained by alternately bonding ethylene oxide and carbon dioxide, which does not contain an ether bond component detectable by ¹ H-NMR analysis.

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