Production and use of supported quaternary phosphonium catalyst

Abstract

Method for generating a supported quaternary phosphonium catalyst, comprising a step of reacting a tertiary phosphine of the following formula (2) with a macromolecular agent of the following formula (3), wherein the weight ratio of tertiary phosphine to the macromolecular mean is 1 to 20:80 to 99, preferably 1 to 15:85 to 99, wherein R1, R2 and R3 are identical or different from each other and are each independently selected from the group consisting of an optionally substituted straight-chain or branched C 1-20 -Alkyl, optionally substituted straight-chain or branched C 2-20 -Alkenyl, optionally substituted straight-chain or branched C 2-20 -Alkynyl, optionally substituted C 3-20 -Cycloalkyl or optionally substituted C 6-20 -Aryl, preferably straight-chain or branched C 2-10 -Alkyl, straight-chain or branched C 2-10-Alkyl, substituted by one or more phenyl or C 3-20 -Cycloalkyl, straight-chain or branched C 2-10 -Alkenyl, straight-chain or branched C 2-10 -Alkenyl, substituted by one or more phenyl or C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl, substituted by one or more straight-chain or branched C 2-6 -Alkyl or straight-chain or branched C 2-6 -Alkenyl, C 6-20 -Aryl or C 6-20 -Aryl, substituted by one or more straight-chain or branched C 1-6 -Alkyl or straight-chain or branched C 2-6 -Alkenyl, - a covalent bond, where X is a halogen atom preferably Cl, Br or I, more preferably Br or I, L is a bivalent bonding group, preferably selected from the group consisting of optionally substituted straight-chain or branched C 1-20-Alkylene, optionally substituted straight-chain or branched C 2-20 -Alkenyls or optionally substituted straight-chain or branched C 2-20 -Alkynyls, more preferably from the group consisting of a straight-chain or branched C 1-20 -Alkylenes, more preferably selected from the group consisting of straight-chain C 2-8 -Alkylene, wherein the alkylene, alkenylene or alkynylene is optionally modified by one or more, for example 1 to 3, 1 to 2 or one, intermediate groups, selected from the group consisting of -O-, -S-, -NR a -, where R a C 1-4 -Alkyl is, and phenylene, preferably phenylene, a carrier is preferably one or more selected from the group consisting of an organic support and an inorganic support, more preferably one or more selected from the group consisting of an inorganic support, more preferably one or more selected from the group consisting of silica, zeolite, preferably SBA-15, MCM-41, MCF, HMS, KIT-6 or SBA-16, and diatomaceous earth, - a covalent bond is, where the reaction temperature is 100 to 190°C and the reaction time is 10 to 40 hours.

Description

Technical area

[0001] This invention relates to a process for producing a supported quaternary phosphonium catalyst and the use thereof in the production of dialkyl carbonates. Background of the invention

[0002] Dialkyl carbonates (especially dimethyl carbonate) are extensively used in the chemical industry. With relatively mild reaction conditions, high yield, and co-production of glycols, the transesterification process is considered the most promising process in the industry for the production of dialkyl carbonates.

[0003] Generally, the transesterification reaction requires an alkali metal hydroxide, alkali metal carbonate, or alkali metal alkoxylate as a catalyst, which are homogeneous and therefore difficult to separate from the reaction products. A catalyst formed by supporting an alkali metal or alkali metal salt on a support is sensitive to water and CO2 in the air, which can significantly reduce the catalyst activity. Metal oxide-type catalysts, alkaline earth metal-exchanged zeolite-type catalysts, or clay-type catalysts suffer from relatively low activity or selectivity. Ion-exchange resin-type catalysts, such as quaternary amine- or tertiary amine-based catalysts, suffer from unstable catalyst activity because the nitrogen elements they contain are easily leached after long-term use.

[0004] Therefore, there is still a need in the art for a catalyst for the production of dialkyl carbonates that can be produced by a simple and industrially advantageous process and that effectively overcomes the above-mentioned disadvantages of prior art catalysts. Tian et al. (Green Chem. 2007, 9, 566-571) report a synthesis of dimethyl carbonate from methanol, propylene oxide, and CO2, catalyzed by a recyclable polyethylene glycol functionalized with an inorganic base and a phosphonium nalide. Takahashi et al. (Chem. Comm, 2006, 1664-1666) report a synergistic hybrid catalyst that can be used for the synthesis of cyclic carbonates. The reported catalyst is based on a phosphonium salt supported on diatomaceous earth.US2008 / 0214386 A1 discloses a similar solid catalyst based on an ionic substance containing a Group 15 element and an inorganic solid. Summary of the invention

[0005] These inventors conducted an intensive study on the prior art and finally found a specific supported quaternary phosphonium catalyst which is characterized by a relatively high and stable catalyst activity and, when used as a catalyst in the production of dialkyl carbonates as a transesterification process, can effectively overcome the above-mentioned disadvantages with respect to prior art catalysts, thereby achieving this invention.

[0006] Specifically, this invention relates to the following aspects: 1. In a reference aspect, a supported quaternary phosphonium catalyst having the following average molecular structure (1): wherein X is a halogen atom (preferably Cl, Br or I, more preferably Br or I), R1, R2 and R3 are different or identical to each other and are each independently selected from the group consisting of an optionally substituted straight-chain or branched C 1-20 -alkyl, optionally substituted straight-chain or branched C 2-20 -Alkenyl, optionally substituted straight-chain or branched C 2-20 -alkynyl, optionally substituted C 3-20 -cycloalkyl or optionally substituted C 6-20 -aryl (preferably straight-chain or branched C 2-10 -Alkyl, straight-chain or branched C 2-10 -Alkyl substituted by one or more phenyl or C 3-20 -Cycloalkyl, straight-chain or branched C 2-10 -Alkenyl, straight-chain or branched C 2-10-Alkynyl, substituted by one or more phenyl or C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl substituted by one or more straight-chain or branched C 1-6 -Alkyl or straight-chain or branched C 2-6 -Alkenyl, C 6-20 -aryl or C 6-20 -aryl substituted by one or more straight-chain or branched C 1-6 -Alkyl or straight-chain or branched C 2-6 -alkenyl), L is a divalent linking group (preferably selected from the group consisting of optionally substituted straight-chain or branched C 1-20 -alkylene, optionally substituted straight-chain or branched C 2-20 -alkenylene or optionally substituted straight-chain or branched C 2-20 -alkynylene, more preferably from the group consisting of a straight-chain or branched C 1-20 -alkylene, more preferably selected from the group consisting of straight-chain C 2-8-Alkylene, wherein the alkylene, alkenylene or alkynylene is optionally modified by one or more (for example 1-3, 1-2 or one) intermediate group selected from the group consisting of -O-, -S-, -NR a - (R a is C 1-4 -alkyl) and phenylene (preferably phenylene)), a carrier is (preferably one or more selected from the group consisting of an organic carrier and inorganic carrier, more preferably one or more selected from the group consisting of an inorganic carrier, more preferably one or more selected from the group consisting of silica, zeolite (preferably SBA-15, MCM-41, MCF, HMS, KIT-6 or SBA-16) and diatomaceous earth), - is a covalent bond, • is an ionic bond, n is an average number such that the weight ratio of the moiety (also referred to as quaternary phosphonium group) to the moiety (carrier) is 1-25:75-99, preferably 1-20:80-99.2. In a further reference aspect, a supported quaternary phosphonium catalyst according to any one of the above aspects having an elution loss D of less than 2%, preferably less than 1.5%, more preferably less than 1%, more preferably less than 0.8%, further preferably less than 0.5%, wherein the elution loss D is determined by a method comprising weighing 2 g of the supported quaternary phosphonium catalyst having a P content of P1 (unit: wt.%), (1) suspending the supported quaternary phosphonium catalyst in 40 ml of methanol, stirring (at a stirring speed of 100 rpm) the resulting mixture at 100°C for 4 hours, then immediately filtering the resulting mixture to separate the supported quaternary phosphonium catalyst, (2) then suspending the separated supported quaternary phosphonium catalyst in 40 ml of methanol, stirring (at a stirring speed of 100 rpm) the resulting mixture at 100°C for 4 hours, then immediately filtering the resulting mixture to separate the supported quaternary phosphonium catalyst, repeating the procedure (2) for another 10 times, and then determining the P content of the finally separated supported quaternary phosphonium catalyst as P2 (Unit: wt%), and then calculating the elution loss D as follows:. D=(P1−P2) / P1×100%. 3. A process for producing a supported quaternary phosphonium catalyst, comprising a step of reacting a tertiary phosphine having the following formula (2) with a macromolecular agent of the following formula (3), wherein the weight ratio of the tertiary phosphine to the macromolecular agent is 1-20:80-99, preferably 1-15:85-99, wherein R1, R2 and R3 are identical or different from each other and are each independently selected from the group consisting of an optionally substituted straight-chain or branched C 1-20 -alkyl, optionally substituted straight-chain or branched C 2-20 -alkenyl, optionally substituted straight-chain or branched C 2-20 -alkynyl, optionally substituted C 3-20 -cycloalkyl or optionally substituted C 6-20 -aryl (preferably straight-chain or branched C 2-10 -Alkyl, straight-chain or branched C 2-10 -Alkyl substituted by one or more phenyl or C3-20 -Cycloalkyl, straight-chain or branched C 2-10 -Alkenyl, straight-chain or branched C 2-10 -Alkenyl, substituted by one or more phenyl or C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl substituted by one or more straight-chain or branched C 2-6 -Alkyl or straight-chain or branched C 2-6 -Alkenyl, C 6-20 -aryl or C 6-20 -aryl substituted by one or more straight-chain or branched C 1-6 -alkyl or straight-chain or branched C 2-6 -alkenyl), - is a covalent bond, wherein X is a halogen atom (preferably Cl, Br or I, more preferably Br or I), L is a divalent linking group (preferably selected from the group consisting of optionally substituted straight-chain or branched C 1-20 -Alkylene, optionally substituted straight-chain or branched C 2-20-alkenylene or optionally substituted straight-chain or branched C 2-20 -alkynylene, more preferably from the group consisting of a straight-chain or branched C 1-20 -alkylene, more preferably selected from the group consisting of straight-chain C 2-8 -Alkylene, wherein the alkylene, alkenylene or alkynylene is optionally modified by one or more (for example 1 to 3, 1 to 2 or one) intermediate group selected from the group consisting of -O-, -S-, -NR a - (R a is C 1-4-alkyl) and phenylene (preferably phenylene)), a carrier is (preferably one or more selected from the group consisting of an organic carrier and inorganic carrier, more preferably one or more selected from the group consisting of an inorganic carrier, more preferably one or more selected from the group consisting of silica, zeolite (preferably SBA-15, MCM-41, MCF, HMS, KIT-6 or SBA-16) and diatomaceous earth), - is a covalent bond, wherein the reaction temperature is 100 to 190°C and the reaction time is 10 to 40 hours. 4. A process according to any one of the above aspects, wherein the reaction temperature is 120 to 190°C and the reaction time is 10 to 30 hours. 5. A process according to any one of the above aspects, wherein the support is one or more selected from the group consisting of silica, zeolite (preferably SBA-15, MCM-41, MCF, HMS, KIT-6 or SBA-16) and diatomaceous earth, and the macromolecular agent is produced by a reaction between the support and a halogenating agent of the following formula (4), wherein the weight ratio of the halogenating agent to the support is 0.005-0.15:1, preferably 0.01-0.1:1, wherein X is a halogen atom (preferably Cl, Br or I, more preferably Cl), L is a divalent linking group (preferably selected from the group consisting of an optionally substituted straight-chain or branched C 1-20 -Alkylene, optionally substituted with straight-chain or branched C 2-20 -alkenylene or optionally substituted straight-chain or branched C 2-20 -alkynylene, more preferably selected from the group consisting of a straight-chain or branched C 1-20-alkylene, more preferably selected from the group consisting of a straight-chain C 2-8 -Alkylene, wherein the alkylene, alkenylene or alkynylene may optionally contain one or more (for example 1 to 3, 1 to 2 or one) groups selected from the group consisting of -O-, -S-, -NR a - (R a is C 1-4 -alkyl) and phenylene (preferably phenylene)), M is Ti, Si or Zr, preferably Si, R4, R5 and R6 are identical or different from each other and are each independently selected from the group consisting of straight-chain or branched C 1-4 -Alkoxy, preferably methoxy or ethoxy. 6. A process according to any one of the above aspects, wherein in the reaction between the support and the halogenating agent the reaction temperature is 70 to 140°C, preferably 90 to 120°C and the reaction time is 1 to 60 hours, preferably 5 to 48 hours. 7. A process according to any one of the preceding aspects, wherein X is Cl and the process further comprises a step of contacting the macromolecular agent with one or more modifiers selected from the group consisting of a brominating agent (preferably alkali metal bromide, more preferably one or more selected from the group consisting of LiBr, NaBr, KBr and CsBr) and an iodizing agent (preferably an alkali metal iodide, more preferably one or more selected from the group consisting of LiI, NaI, KL and CsI) prior to the reaction of the macromolecular agent with the tertiary phosphine, wherein the weight ratio of the modifier to the macromolecular agent is 0.01-1:1, preferably 0.02-0.6:1. 8. Use of the supported quaternary phosphonium catalyst of a supported quaternary phosphonium catalyst produced according to the process according to any one of the above aspects as a catalyst in the co-production of a Di -C 1-10 -alkyl carbonate and a C 2-10 -alkanediols by a transesterification process. 9. A process for producing a dialkyl carbonate, comprising a step of contacting a C 2-10 -alkylene carbonate (preferably ethylene carbonate or propylene carbonate) with a monovalent C 1-10 -alcohol (preferably methanol) in the presence of a supported quaternary phosphonium catalyst produced according to the process of any of the above aspects to produce a di-C 1-10 -alkyl carbonate (preferably dimethyl carbonate) and a C 2-10 -alkanediols (preferably ethylene glycol or propylene glycol). 10. A process according to any one of the above aspects, wherein the reaction temperature is 60 to 140°C, preferably 80 to 140°C, the reaction time is 0.1-20 hours, preferably 1-10 hours, the molar ratio of the monovalent C 1-10 -alkanol to C 2-10-Alkylene carbonate 2 to 10:1, preferably 2 to 6:1 and the weight ratio of the supported quaternary phosphonium catalyst to the C 2-10 -Alkylene carbonate is 0.005 to 0.5:1, preferably 0.01 to 0.2:1. Technical effects

[0007] The supported quaternary phosphonium catalyst according to this disclosure has the following advantages.

[0008] According to this disclosure, the supported quaternary phosphonium catalyst is physically / chemically stable and therefore does not degrade even after long-term storage, which facilitates further use.

[0009] The supported quaternary phosphonium catalyst is stable and steady in terms of catalyst activity, less susceptible to degradation by reaction conditions or normal environments, and even after long-term use or many times of recycling, the activity thereof is maintained to a significant extent (decreased by less than 5%, preferably less than 2%).

[0010] According to this disclosure, in the supported quaternary phosphonium catalyst, the active catalyst group (quaternary phosphonium group) bonds with the support through a strong chemical bond (covalent bond), thereby achieving a firm and strong bond therebetween, and even after long-term use or many times of recycling, the active catalyst group is not detached to a significant extent.

[0011] According to this disclosure, the supported quaternary phosphonium catalyst can be easily regenerated even if the catalyst activity decreases to an unacceptable level and is therefore characterized by low costs in both production and use.

[0012] According to this disclosure, by controlling the loading / density of the XL- group on the macromolecular agent and / or by controlling the ratio of the tertiary phosphine to the macromolecular agent to be used, it is easy to control the loading / density of the quaternary phosphonium group on the support, thereby freely controlling the catalyst activity of the supported quaternary phosphonium catalyst.

[0013] According to this disclosure, the catalyst activity and selectivity of the supported quaternary phosphonium catalyst are so high that when used as a catalyst in the production of dialkyl carbonates by a transesterification process, it is possible to co-produce dialkyl carbonates and glycols in high yield.

[0014] According to one embodiment of this disclosure, when the supported quaternary phosphonium catalyst was used as a catalyst in the production of dimethyl carbonate by transesterification reaction of ethylene carbonate with methanol under the conditions of a reaction temperature of 100°C, a molar ratio of methanol to ethylene carbonate of 4:1, a weight ratio of the catalyst to ethylene carbonate of 0.05:1, and a reaction time of 4 hours, the ethylene carbonate conversion was 49.2%, the selectivity to dimethyl carbonate was 98.9%, the selectivity to ethylene glycol was 98.7%, and after 5 times of recycling, the catalyst activity decreased by less than 2%. Best mode for carrying out the invention

[0015] This invention will be described in detail with reference to the following specific embodiments. However, it should be understood that the scope of this invention should not be limited to these specific embodiments, but should instead be determined by the appended claims.

[0016] In the context of this specification, when a material, process / step, part, system or device is described as "known to a person skilled in the art" or "commonly known in the art" or the like, it is meant that it is commonly used in the art on the date this application is filed and further that it has not been widely used in the art up to that date, but is intended for a similar purpose.

[0017] In the context of this description, the term “halogen atom” refers to F, Cl, Br and I.

[0018] In the context of this description, the term “optionally substituted” refers to optionally substituted by one or more (for example 1-5, 1-4, 1-3, 1-2 or 1) substituents selected from the group consisting of a halogen atom, straight-chain or branched C 1-6 -alkyl, straight-chain or branched C 1-6 -Haloalkyl, straight-chain or branched C 2-6 -alkenyl, straight-chain or branched C 2-6 -alkynyl, straight-chain or branched C 1-6 -Alkoxy, C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl-straight-chain or branched C 1-6 -Alkyl, C 3-20 -Cycloalkyl-straight-chain or branched C 1-6 -Alkoxy, C 6-20 -Aryl, C 6-20 -aryl-straight-chain or branched C 1-6 -alkyl and C 6-20 -aryl-straight-chain or branched C 1-6 -Alkoxy. The substituent is the halogen atom, the straight-chain or branched C 1-6 -Alkyl, C 3-20 -Cycloalkyl, C3-20 -Cycloalkyl-straight-chain or branched C 1-6 -Alkyl, C 6-20 -aryl or C 6-20 -aryl-straight-chain or branched C 1-6 -Alkyl is more preferred, where C 3-20 -Cycloalkyl or C 6-20 -aryl is more preferred.

[0019] In the context of this description, the term ‘C 3-20 -Cycloalkyl" means a monocyclic, bicyclic or polycyclic alkyl having a ring carbon atom number of 3 to 20. For example, a monocyclic alkyl such as cyclohexyl, cyclopropyl and cyclopentyl and a spiro-, bridged or fused bicyclic or polycyclic alkyl such as biscyclopentyl, decalinyl, adamantanyl, spiro[2.4]heptyl, spiro[4.5]decyl, bicyclo[3.2.1]octanyl, tricyclo[2.2.1.0 2,6 ]octanyl or norbornanyl. As C 3-20 -Cycloalkyl is the monocyclic C 5-10 -Alkyl is more preferred.

[0020] In the context of this description, the term ‘C 6-20 -Aryl" is an aromatic hydrocarbyl having a ring carbon atom number of 6 to 2. For example, phenyl, a group obtained by directly bonding two or more (for example, 2-6, 2-5, 2-4, or 2-3) benzene rings through a single bond, for example, biphenyl and triphenyl, and a group obtained by fusing two or more (for example, 2-6, 2-5, 2-4, or 2-3) benzene rings, for example, naphthyl, anthryl, or phenanthryl, can be illustrated. As C 6-20 -Aryl, phenyl, biphenyl and naphthyl are more preferred, phenyl is further preferred.

[0021] In the context of this specification, the term "conversion" refers to single-pass conversion, i.e., the conversion observed after a single contact of the reactant (e.g., ethylene carbonate) with the catalyst. Similarly, in the context of this specification, the term "selectivity" refers to single-step selectivity.

[0022] Finally, any percentage, ratio, portion or the like mentioned in the context of this description is intended to be calculated on a weight basis unless otherwise explicitly stated or a weight basis appears unlikely to the person skilled in the art.

[0023] Specifically, in one reference aspect, this disclosure relates to a supported quaternary phosphonium catalyst having the following average molecular structure (1): wherein X is halogen atom, R1, R2 and R3 are identical or different from each other and are each independently selected from the group consisting of an optionally substituted straight-chain or branched C 1-20 -alkyl, optionally substituted, straight-chain or branched C 2-20 -Alkenyl, optionally substituted, straight-chain or branched C 2-20 -alkynyl, optionally substituted C 3-20 -cycloalkyl or optionally substituted C 6-20 -aryl, L is a divalent linking group, is a support, - is a covalent bond, • is an ionic bond, n is an average number such that the weight ratio of the moiety (also called quaternary phosphonium group) to the moiety (support) is 1-25:75 to 99.

[0024] According to this disclosure, X preferably represents Cl, Br or I, more preferably Br or I.

[0025] According to this disclosure, R1, R2 and R3 are preferably identical or different from one another and are each independently selected from the group consisting of a straight-chain or branched C 2-10 -alkyl, straight-chain or branched C 2-10 -Alkyl substituted by one or more (for example 1-4, 1-3, 1-2 or 1) phenyl or C 3-20 -Cycloalkyl, straight-chain or branched C 2-10 -alkenyl (for example allyl), straight-chain or branched C 2-10 -Alkenyl substituted by one or more (for example 1-4, 1-3, 1-2 or 1) phenyl or C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl substituted by one or more (for example 1-4, 1-3, 1-2 or 1) straight-chain or branched C 1-6 -alkyl or straight-chain or branched C 2-6 -Alkynyl, C 6-20-aryl (for example phenyl) or C 6-20 -aryl substituted by one or more straight-chain or branched C 2-6 -Alkenyl. According to this disclosure, L is preferably selected from the group consisting of an optionally substituted straight-chain or branched C 1-20 -alkylene, optionally substituted straight-chain or branched C 2-20 -alkenylene or optionally substituted straight-chain or branched C 2-20 -alkynylene.

[0026] According to this disclosure, L is more preferably selected from the group consisting of a straight-chain or branched C 2-10 -alkylene, more preferably straight-chain C 2-8 -alkylene.

[0027] According to this disclosure, the alkylene, alkenylene or alkynylene in L may optionally be interrupted by one or more (for example 1-3, 1-2 or 1) intervening groups selected from the group consisting of -O-, -S-, -NR a - (R ais C 1-4 -alkyl) and phenylene at any appropriate position. Phenylene is preferred as the intervening group. When two or more exist, any two intervening groups (excluding phenylene) are not directly bonded to each other. By "interposed" or intervening, it is meant that the intervening group affects the main molecular chain of the alkylene, alkenylene, or alkynylene, thereby forming part of the main chain, with positions appropriate for this penetration including the interior and each end of the molecular chain. For example, the group -CH2-CH2-CH2-CH2-, by insertion of one phenylene group, results in - CH2-phenylene-CH2-CH2-CH2, -CH2-CH2-phenylene-CH2-CH2-, -CH2-CH2-CH2-phenylene-CH2, -CH2-CH2-CH2-CH2-phenylene- or -phenylene-CH2-CH2-CH2-CH2-.

[0028] According to this disclosure, it is preferably selected from an organic carrier and an inorganic carrier, more preferably an inorganic carrier. These carriers can be used in one type or as a mixture of two or more types.

[0029] According to this disclosure, as the organic carrier, olefin homopolymers or copolymers, vinyl alcohol homopolymers or copolymers, cyclodextrins, polyesters or copolyesters, polyamides or copolyamides, vinyl chloride homopolymers or copolymers, acrylic homopolymers or copolymers, methacrylic homopolymers or copolymers, styrene homopolymers or copolymers, and partially crosslinked products of these homopolymers or copolymers can be exemplified, preferably partially crosslinked styrene polymers (for example, one with a crosslinking degree of 2 to less than 100%). These organic carriers can be used in one kind or as a mixture of two or more kinds.

[0030] According to this disclosure, the inorganic support exemplified may be a refractory oxide of a metal from Group IIA, IIIA, IVA, or IVB of the Periodic Table of Elements (e.g., silica, alumina, magnesia, titania, zirconia, or thorium oxide) or a refractory composite oxide of any two or more of these metals (e.g., silica-alumina, magnesia-alumina, titania-silica, titania-magnesia, or titania-alumina) and clay, zeolite (e.g., SBA-15, MCM-41, MCF, HMS, KIT-6, or SBA-16), mica, montmorillonite, bentonite, or diatomaceous earth. These inorganic supports may be used in one type or as a mixture of two or more types.

[0031] As the inorganic carrier, preference is given to one or more selected from the group consisting of silica, zeolite (preferably SBA-15, MCM-41, MCF, HMS, KIT-6 or SBA-16) and diatomaceous earth.

[0032] According to this disclosure, the average value n is preferably such that the weight ratio of the quaternary phosphonium group to the support is 1 to 20:80 to 99.

[0033] According to this disclosure, the elution loss D of the supported quaternary phosphonium catalyst is less than 2%, preferably less than 1.5%, more preferably less than 1%, more preferably less than 0.8%, further preferably less than 0.5%. Therefore, in the supported quaternary phosphonium catalyst of this disclosure, the active catalyst components (the quaternary phosphonium groups) bond strongly and tightly with the support and are not easily detached therefrom, resulting in constant and stable catalyst performance.

[0034] According to this disclosure, the elution loss D is determined according to a method comprising the following steps: weighing 2 g of the supported quaternary phosphonium catalyst having a P content of Pl (unit: wt.%), (1) suspending the supported quaternary phosphonium catalyst in 40 ml of methanol, stirring (at a stirring speed of 100 rpm) the resulting mixture at 100°C for 4 hours, then immediately filtering the resulting mixture to separate the supported quaternary phosphonium catalyst, (2) then suspending the separated supported quaternary phosphonium catalyst in 40 ml of methanol, stirring (at a stirring speed of 100 rpm) the resulting mixture at 100°C for 4 hours, then immediately filtering the resulting mixture to separate the supported quaternary phosphonium catalyst, repeating the procedure (2) for another 10 times, and then determining the P content of the finally separated supported quaternary phosphonium catalyst as P2 (Unit: wt%) and then calculating the elution loss D as follows:. D=(P1−P2) / P1×100%

[0035] According to this disclosure, the P content can be determined using an XRF method. For example, this determination can be performed on the S4 PIONEER X-ray fluorescence spectrometer (manufactured by Bruker) using a standardless and semi-quantitative method.

[0036] The supported quaternary phosphonium catalyst can be prepared, for example, by the following process according to the invention.

[0037] According to this invention, the process comprises a step of reacting a tertiary amine having the following formula (2) with a macromolecular agent having the following formula (3).wherein R1, R2 and R3 are identical or different from each other and are each independently selected from the group consisting of an optionally substituted, straight-chain or branched C 1-20 -alkyl, optionally substituted, straight-chain or branched C 2-20-Alkenyl, optionally substituted or straight-chain or branched C 2-20 -alkynyl, optionally substituted C 3-20 -cycloalkyl or optionally substituted C 6-20 -aryl, -- is a covalent bond.wherein X is a halogen atom, L is a divalent linking group,is a carrier, -- is a covalent bond.

[0038] According to this invention, the reaction can be carried out in the presence of a solvent. As a solvent, any chemically inert solvent capable of dissolving the tertiary phosphine can be exemplified, for example, a nitrile-based solvent, for example, acetonitrile or benzonitrile, with benzonitrile being more preferred. These solvents can be used in one type or as a mixture of two or more types.

[0039] According to this invention, for carrying out the reaction, the reaction temperature is 100 to 190°C, preferably 120 to 190°C and the reaction time is 10 to 40 hours, preferably 10 to 30 hours.

[0040] According to this invention, for carrying out the reaction, the weight ratio of the tertiary amine to the macromolecular agent 1 is 20:80 to 99, preferably 1-15:85 to 99.

[0041] According to this invention, upon completion of the reaction, it is easy to separate the supported quaternary phosphonium catalyst from the reaction mixture by a separation method known in the art. Examples of separation methods include, but are not limited to, filtration, washing (e.g., washing with the reaction solvent, ethanol, or acetone for 2 to 6 times, 2 to 5 times, 2 to 4 times, or 2 to 3 times), and drying (e.g., drying under vacuum at 60 to 100°C for 4 to 20 hours).

[0042] According to this invention, X is preferably Cl, Br or I, more preferably Br or I.

[0043] According to this invention, R1, R2 and R3 are preferably identical or different from one another and are each independently selected from the group consisting of a straight-chain or branched C 2-10 -alkyl, straight-chain or branched C 2-10 -Alkyl substituted by one or more (for example 1-4, 1-3, 1-2 or 1) phenyl or C 3-20 -Cycloalkyl, straight-chain or branched C 2-10 -Alkenyl (for example allyl), straight-chain or branched C 2-10 -Alkenyl substituted by one or more (for example 1-4, 1-3, 1-2 or 1) phenyl or C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl substituted by one or more (for example 1-4, 1-3, 1-2 or 1) straight-chain or branched C 1-6 -Alkyl or straight-chain or branched C 2-6 -Alkenyl, C 6-20-aryl (for example phenyl) or C 6-20 -aryl substituted by one or more (for example 1-4, 1-3, 1-2 or 1) straight-chain or branched C 1-6 -Alkyl or straight-chain or branched C 2-6 -Alkenyl. According to this invention, L is preferably selected from the group consisting of an optionally substituted straight-chain or branched C 1-20 -alkylene, optionally substituted, straight-chain or branched C 2-20 -alkenylene or optionally substituted straight-chain or branched C 2-20 -alkynylene.

[0044] According to this invention, L is more preferably selected from the group consisting of a straight-chain or branched C 1-20 -alkylene, more preferably straight-chain C 2-8 -alkylene.

[0045] According to this invention, the alkylene, alkenylene or alkynylene in the L may optionally be interrupted by one or more (for example 1-3, 1-2 or 1) intervening groups selected from the group consisting of -O-, -S-, -NR a - (R a is a C 1-4-alkyl) and phenylene at any appropriate position. Phenylene is preferred as the intervening group. When two or more exist, generally any two of the intervening groups (excluding phenylene) are not directly bonded to each other. Herein, "interposed" or "intermediate" means that the intervening group enters the main molecular chain of alkylene, alkenylene, or alkynylene, thereby forming part of the main chain, with positions appropriate for this interposition including the interior and each end of the molecular chain. For example, the group -CH2-CH2-CH2-CH2-after insertion of a phenylene group leads to -CH2-phenylene-CH2-CH2-CH2, -CH2-CH2-phenylene-CH2-CH2-, -CH2-CH2-CH2-phenylene-CH2, -CH2-CH2-CH2-CH2-phenylene- or -phenylene-CH2-CH2-CH2-CH2-CH2 - .

[0046] According to this invention, it is preferably selected from an organic carrier and inorganic carrier, more preferably an inorganic carrier.

[0047] These supports can be used with one species or as a mixture of two or more species.

[0048] According to this invention, exemplified as organic carriers are olefin homopolymers or copolymers, vinyl alcohol homopolymers or copolymers, cyclodextrins, polyesters or copolyesters, polyamides or copolyamides, vinyl chloride homopolymers or copolymers, acrylic homopolymers or copolymers, methacrylic homopolymers or copolymers, styrene homopolymers or copolymers, and partially crosslinked products of these homopolymers or copolymers, preferably partially crosslinked styrene polymers (for example, one with a crosslinking degree of 2 to less than 100%). These organic carriers can be used in one kind or as a mixture of two or more kinds.

[0049] According to this invention, as the inorganic carrier, there can be exemplified a refractory oxide of a metal of Group IIA, IIIA, IVA, or IVB of the Periodic Table of Elements (e.g., silica, alumina, magnesia, titania, zirconia, or thoria) or a refractory composite oxide of any two or more of these metals (e.g., silica-alumina, magnesia-alumina, titania-silica, titania-magnesia, or titania-alumina) and clay, zeolite (e.g., SBA-15, MCM-41, MCF, HMS, KIT-6, or SBA-16), mica, montmorillonite, bentonite, or diatomaceous earth. These inorganic carriers can be used in one type or as a mixture of two or more types.

[0050] As the inorganic carrier, preference is given to one or more selected from the group consisting of silica, zeolite (preferably SBA-15, MCM-41, MCF, HMS, KIT-6 OR SBA-16) and diatomaceous earth.

[0051] According to this invention, the macromolecular agent can be produced by reacting the carrier with a halogenating agent having the following formula (4). wherein X is a halogen atom, L is a divalent linking group, M is Ti, Si or Zr, preferably Si, R4, R5 and R6 are identical or different from each other and are each independently selected from the group consisting of a straight-chain or branched C 1-4 -Alkoxy, preferably methoxy or ethoxy.

[0052] According to this invention, X is preferably Cl, Br or I, more preferably Cl.

[0053] According to this invention, L is preferably selected from the group consisting of an optionally substituted straight-chain or branched C 1-20-alkylene, optionally substituted straight-chain or branched C 2-20 -alkenylene or optionally substituted straight-chain or branched C 2-20 -alkynylene.

[0054] According to this invention, L is more preferably selected from the group consisting of a straight-chain or branched C 1-20 -alkylene, more preferably straight-chain C 2-8 -alkylene.

[0055] According to this invention, the alkylene, alkenylene, or alkynylene in the L may optionally be interrupted by one or more (for example 1-3, 1-2 or 1) intermediate groups selected from the group consisting of -O-, -S-, -NR a -(R a is C 1-4-alkyl) and phenylene at any appropriate position. Phenylene is preferred as the intervening group. When two or more exist, generally any two of the intervening groups (excluding phenylene) do not bond directly to each other. By "interposed" or "intervening" is meant that the intervening group interrupts the main molecular chain of the alkylene, alkenylene, or alkynylene, thereby forming part of the main chain, with appropriate positions for this interruption including the interior or any end of the molecular chain. For example, the group -CH2-CH2-CH2-CH2- after insertion of a phenylene group leads to -CH2-phenylene-CH2-CH2-CH2, -CH2-CH2-phenylene-CH2-CH2-, -CH2-CH2-CH2-phenylene-CH2, -CH2-CH2-CH2-CH2-phenylene- or -phenylene-CH2-CH2-CH2-CH2-CH2-.

[0056] According to this invention, for carrying out the reaction, the reaction temperature may be 70 to 140°C, preferably 90 to 120°C, and the reaction time should be 1-60 hours, preferably 5 to 48 hours.

[0057] According to this invention, for carrying out the reaction, the weight ratio of the halogenating agent to the carrier may be 0.005 to 0.15:1, preferably 0.01-0.1:1.

[0058] According to this invention, the reaction can be carried out in the presence of a solvent. As the reaction solvent, any chemically inert solvent that can dissolve the halogenating agent can be exemplified, for example, an aromatic C 6-12 -hydrocarbon or halogenated aromatic C 6-12 -hydrocarbon. Specifically, toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorinated toluene, chlorinated ethylbenzene, brominated toluene, and brominated ethylbenzene can be exemplified. The aromatic C6-12 Hydrocarbon or toluene is preferred. These solvents can be used in one type or as a mixture of two or more types.

[0059] According to this invention, an organic or inorganic carrier is preferred, more preferably an inorganic carrier. These carriers can be used in one kind or as a mixture of two or more kinds. According to this invention, as the organic carrier, there can be exemplified olefin homopolymers or copolymers, vinyl alcohol homopolymers or copolymers, cyclodextrins, polyesters or copolyesters, polyamides or copolyamides, vinyl chloride homopolymers or copolymers, acrylic homopolymers or copolymers, methacrylic homopolymers or copolymers, styrene homopolymers or copolymers, and partially crosslinked products of these homopolymers or copolymers, preferably partially crosslinked styrene polymers (for example, one having a crosslinking degree of 2 to less than 100%). These organic carriers can be used alone or as a mixture of two or more kinds.

[0060] According to this invention, as the inorganic carrier, there can be exemplified a refractory oxide of a metal of Group IIA, IIIA, IVA, or IVB of the Periodic Table of Elements (e.g., silica, alumina, magnesia, titania, zirconia, or thoria) or a refractory composite oxide of any two or more of these metals (e.g., silica-alumina, magnesia-alumina, titania-silica, titania-magnesia, or titania-alumina) and clay, zeolite (e.g., SBA-15, MCM-41, MCF, HMS, KIT-6, or SBA-16), mica, montmorillonite, bentonite, or diatomaceous earth. These inorganic carriers can be used alone or as a mixture of two or more types.

[0061] As the inorganic carrier, preference is given to one or more selected from the group consisting of silica, zeolite (preferably SBA-15, MCM-41, MCF, HMS, KIT-9 or SBA-16) and diatomaceous earth.

[0062] According to this invention, a suitable silicon oxide can be produced by any conventional method or is a commercially available one.

[0063] According to this invention, the specific surface area (according to BET method) of the support can be 100 to 1500 m 2 / g, preferably 200 to 1000 m 2 / g, while the average particle size (measured by a laser particle size analyzer) thereof may be 1 to 500 mm, preferably 1 to 100 mm. According to this invention, the carrier may be in any form, for example, as fine powder, particles, spheres, aggregates, or other forms.

[0064] According to this invention, the inorganic carrier is preferred as the carrier. Generally, an inorganic carrier carries active functional groups, such as hydroxyl groups, on its surface. The macromolecular agent can be produced by reacting these active functional groups with the alkoxy groups on the halogenating agent.

[0065] According to one embodiment of this invention, the inorganic support may be subjected to thermal activation prior to use to enhance or modify the activity of these active functional groups. The thermal activation may be carried out in a conventional manner. For example, the inorganic support is treated with heat under reduced pressure or under an inert gas atmosphere. By an inert gas atmosphere, it is meant that no component exists that can react with the inorganic support in the gas atmosphere, or if it exists, it reacts in a relatively small amount. As an inert gas atmosphere, an atmosphere of nitrogen gas or rare earth gas can be exemplified, preferably a nitrogen gas atmosphere.In general, the temperature at which the thermal activation is carried out is from 200 to 800°C, preferably 400 to 700°C, preferably 400 to 650°C, while the duration for the thermal activation is from 0.5 to 24 hours, preferably 2 to 12 hours, more preferably 4 to 8 hours.

[0066] According to this invention, an organic carrier bearing active functional groups such as a hydroxyl group, amino group, sulfo group, or carboxyl group on the surface can also be used as the carrier. In this context, vinyl alcohol homopolymers or copolymers, cyclodextrins, polyesters or copolyesters, polyamides or copolyamides, acrylic homopolymers or copolymers, or methacrylic homopolymers or copolymers can be exemplified. The macromolecular agent can also be produced by reacting these active functional groups with the alkoxy groups on the halogenating agent.

[0067] According to one embodiment of this invention, the organic support may be subjected to thermal activation prior to use to enhance or modify the activation of these active functional groups. The thermal activation may be carried out in a conventional manner. For example, the organic support is treated with heat under reduced pressure or under an inert gas atmosphere. An inert gas atmosphere herein means that no component exists that can react with the organic support in the gas atmosphere, or that, if it exists, reacts only in a relatively small amount. As an inert gas atmosphere, nitrogen gas or rare earth gas atmosphere can be exemplified, preferably a nitrogen gas atmosphere.Given the poor heat resistance, thermal activation should be carried out in conjunction with the organic support with the proviso that the inherent structure and composition of the organic support is not destroyed. Generally, the temperature at which thermal activation is carried out is from 50 to 400°C, preferably 100 to 250°C, while the duration of thermal activation is from 1 to 24 hours, preferably 2 to 12 hours.

[0068] According to this invention, as the macromolecular agent of formula (3), a halogen-containing organic carrier can be used as such. For example, homopolymers of a halogen-containing monomer (for example, vinyl chloride or chlorostyrene) or copolymers of the halogen-containing monomer with a comonomer (for example, ethylene, propylene, styrene, or (meth)acrylic ester), and partially crosslinked products of these homopolymers or copolymers can be exemplified. The XL- group is provided by the halogen-containing organic carrier per se. Furthermore, the macromolecular agent of formula (3) can also be produced by halogenating a halogen-free organic carrier.As the halogen-free organic carrier, olefin homopolymers or copolymers, styrene homopolymers or copolymers, and partially crosslinked products of these homopolymers or copolymers can be exemplified, particularly partially crosslinked styrene polymers (e.g., one having a crosslinking degree of 2 to less than 100%). The method for halogenating (particularly, chlorinating) the halogen-free organic carrier is also known in the polymer field. For example, suspension chlorination or solution chlorination can be exemplified, and further description thereof is omitted. By halogenation, a halo group (e.g., a chloroalkyl group) can be introduced into the halogen-free organic carrier. The group XL- is provided by the halo group.According to this invention, upon completion of the reaction, it is easy to separate the macromolecular agent from the reaction mixture by a separation method commonly known in the field. The separation process can be exemplified by, but is not limited to, filtration, washing (for example, washing with the reaction solvent, ethanol, or methanol for 2 to 6 times, 2 to 5 times, 2 to 4 times, or 2 to 3 times), and drying (for example, drying at 80 to 150°C for 4 to 20 hours).

[0069] According to this invention, when X is Cl, part or all of Cl may optionally be replaced by Br or I. Said process optionally further comprises a step of contacting the macromolecular agent with one or more modifiers selected from the group consisting of a brominating agent and an iodinating agent for one or more times (for example, 2 to 5 times, 2 to 4 times, 2 to 3 times, or 2 times) before reacting the macromolecular agent with the tertiary phosphine.

[0070] According to this invention, for the contact reaction (single contact), the reaction time may be 1 to 4 hours, preferably 1.5 to 4 hours, and the reaction temperature may be 20 to 100°C, preferably normal temperature.

[0071] According to this invention, for the contact reaction (single contact), the weight ratio of the modifier to the macromolecular agent may be 0.01 to 1:1, preferably 0.02 to 0.6:1.

[0072] According to this invention, the contact reaction can be carried out in the presence of a solvent. Examples of reaction solvents include water, alcohols, amides, or ketones, provided that the solvent facilitates the reaction between the modifying agent and the macromolecular agent and is chemically inert, which will be apparent to those skilled in the art.

[0073] According to this invention, upon completion of all contact reactions, it is easy to separate the product (modified macromolecular agent) from the reaction mixture by a separation process commonly known in the art. The separation process can be exemplified by, but is not limited to, filtration, washing (for example, washing with the reaction solvent, water, or methanol for 2 to 6 times, 2 to 5 times, 2 to 4 times, or 2 to 3 times), and drying (for example, drying under vacuum at 60 to 100°C for 4 to 20 hours).

[0074] According to this invention, an alkali metal bromide can be exemplified as the brominating agent, for example, one or more selected from the group consisting of LiBr, NaBr, KBr, and CsBr. An alkali metal iodide can be exemplified as the iodinating agent, for example, one or more selected from the group consisting of LiI, NaI, KL, and CsI. These brominating or iodinating agents can be provided in the form of a solution (particularly in water).

[0075] By the mentioned method, a supported quaternary phosphonium catalyst can be prepared.

[0076] According to this disclosure, the above-mentioned supported quaternary phosphonium catalyst can be easily regenerated when its catalytic activity is reduced to an unacceptable level after use. As the regeneration process, a method comprising a step of reacting the tertiary phosphine of formula (2) with the spent supported quaternary phosphonium catalyst can be exemplified. The method for producing a supported quaternary phosphonium catalyst of this invention can be applied, with the sole exception that part or all of the macromolecular agent can be directly replaced with the spent supported quaternary phosphonium catalyst, thereby regenerating the supported quaternary phosphonium catalyst.

[0077] According to this invention, the phosphonium catalysts produced by the preparation process according to the invention can be used as a catalyst in the production of dialkyl carbonates by a transesterification process. According to a further embodiment of this invention, this invention relates to a process for producing a dialkyl carbonate, comprising a step of contacting a C 2-10 -Alkylene carbonate with a monovalent C 1-10 -alkanol in the presence of this supported quaternary phosphonium catalyst to produce (co-produce) a di-C 1-10 -alkyl carbonate and a C 2-10 -alkanediols.

[0078] According to this invention, C 2-10 -Alkylene carbonate a C 2-5 -Alkylene carbonate is preferred, ethylene carbonate or propylene carbonate is most preferred.

[0079] According to this invention, the monovalent C 1-10 -Alcohol a monovalent C 1-3-Alkanol is preferred, methanol is most preferred.

[0080] According to this invention, by contacting ethylene carbonate (propylene carbonate) with methanol in the presence of the supported quaternary phosphonium catalyst, it is possible to co-produce dimethyl carbonate and ethylene glycol (propylene glycol) in high yield.

[0081] According to this invention, the contacting can be carried out under conditions known in the art in a manner that is normally known in the art. For example, the reaction temperature can be 60 to 140°C, preferably 80 to 140°C, and the reaction time can be 0.1 to 20 hours, preferably 1 to 10 hours, but is not limited thereto. Furthermore, the reaction pressure for contacting can be normal pressure or elevated pressure (for example, the autogenous pressure of the reactor or 0.2-1.5 MPa), but is not limited thereto.

[0082] According to this invention, for contacting, the molar ratio of the monovalent C 1-10 -alkanol to C 2-10 -alkylene carbonate 2 to 10:1, preferably 2 to 6:1 and the weight ratio of the supported quaternary phosphonium catalyst to the C 2-10 -Alkylene carbonate can be 0.005 to 0.5:1, preferably 0.01 to 0.2:1. Examples

[0083] This invention is further illustrated by reference to the following examples, but is not limited thereto. Example 1

[0084] 10.0 g carrier (Aerisol 200, manufactured by Degussa, with a specific surface area of ​​210 m 2 / g) were placed in a 500 ml three-necked flask, and then 200 ml of anhydrous toluene and 2.0 g of γ-chloropropyltriethoxysilane (CPTES, with a molecular structure of C3H6ClSi(OC2H5)3) were added, filtered after refluxing at 110°C for 24 hours, washed 3 times with anhydrous ethanol, and then oven-dried at 110°C for 12 hours to obtain a macromolecular agent.

[0085] Then, the obtained macromolecular agent was added to a solution of 2.0 g of triphenylphosphine in 100 ml of benzonitrile, filtered after 40 hours of reaction at 190°C, washed with ethanol and acetone 3 times, and dried at 60°C in vacuum for 12 hours, and a supported quaternary phosphonium catalyst was obtained. Examples 2 to 9

[0086] Same as Example 1, except that the nature and amount of the support, the nature and amount of the halogenating agent, the reaction temperature and reaction time for producing the macromolecular agent, the nature and amount of the tertiary phosphine, and the reaction temperature and reaction time for producing the supported quaternary phosphonium catalyst were changed as shown in Table 1. Table 1 Macromolecular agent no. carrier Halogenating agents Reaction temperature °C Reaction time h Nature Specific surface area, m 2 / G Quantity g Nature Quantity g A1 Aerosil 200 210 10,0 CPTES 2,0 110 24 A2 Aerosil 200 210 10 , 0 CPTES 2,0 110 24 A3 SBA-15 752 10,0 CPTES 3,0 120 24 A4 MCM-41 1098 10,0 CPTMS a 3,0 80 58 A5 MCF 653 10,0 CPTMS 2,0 120 24 A6 MCF 653 10,0 CPTMS 2,0 120 24 A7 MCF 653 10,0 CBTES b 2,0 120 24 A8 HMS 741 10,0 CBTES 2,0 120 3 A9 HMS 741 10,0 CBTES 2,0 120 24 a: 3-chloropropyltrimethoxysilane with a molecular structure ClC3H6Si(OCH3) 3i b: 4-chloromethylphenyltriethoxysilane, with a molecular structure ClCH2C6H4Si(OC2H5)3. Table 1 (continued) Example No. Tertiary phosphine Reaction time h Reaction temperature °C Macromolecular agent Nature Quantity g 1 Triphenylphosphin 2,0 40 190 A1 2 Triphenylphosphin 0,2 40 190 A2 3 Triphenylphosphin 2,0 40 190 A3 4 Trioctylphosphin 2,0 30 190 A4 5 Phenyldicyclohexylphosphin 2,0 30 170 A5 6 Triethylphosphin 1,5 10 100 A6 7 Allyldiphenylphosphin 0,3 20 150 A7 8 Tributylphosphin 2,0 20 120 A8 9 Tri(2-tolyl)phosphine 2,0 40 190 A9 Example 10

[0087] 5.0 g of the supported quaternary phosphonium catalyst prepared according to Example 1 was added to 100 ml of NaBr solution (0.5 mol / L), left to stand at normal temperature for an exchange time of 2 h, after filtration, the obtained solid was further added to 100 ml of NaBr solution (0.5 mol / L), left to stand at normal temperature for an exchange time of 2 h, after filtration, a supported quaternary phosphonium catalyst was obtained. Example 11

[0088] The procedure of Example 10 was repeated except that each time 100 ml of NaBr solution (0.5 mol / l) was replaced by 100 ml of Kl solution (0.5 mol / l) and the exchange time was changed to 4 h, a supported quaternary phosphonium catalyst was obtained. Examples 12 to 22

[0089] 22.0 g of ethylene carbonate, 32.0 g of methanol, and 1.1 g of a supported quaternary phosphonium catalyst prepared according to any one of Examples 1 to 11 were charged into a 100 ml autoclave (with a molar ratio of methanol to ethylene carbonate of 4:1 and a weight ratio of the supported quaternary phosphonium catalyst to ethylene carbonate of 0.05:1) and reacted at 100°C for 4 h. After completion of the reaction, the autoclave was cooled to room temperature and evacuated. A sample of the liquid phase was withdrawn and subjected to gas chromatography analysis, and the result is shown in Table 2 below, along with the elution loss D (%) determined for each catalyst. Table 2 Example No. Catalyst No. Ethylene carbonate conversion % Dimethyl carbonate selectivity % Ethylene glycol selectivity % Elution loss D % 12 Example 1 49,2 98,9 98,7 0,2 13 Example 2 5,6 96,3 95,8 0,5 14 Example 3 47,5 96,7 95,9 0,6 15 Example 4 41,5 97,1 96,5 0,3 16 Example 5 39,3 95,4 96,1 0,5 17 Example 6 23,1 94,9 95,2 1,0 18 Example 7 9,5 95,6 94,4 0,9 19 Example 8 32,1 97,5 96,1 0,8 20 Example 9 48,2 96,3 95,6 0,8 21 Example 10 45,6 96,5 94,3 0,9 22 Example 11 46,2 98,9 97,1 1,2 Example 23

[0090] The same procedure as in Example 12 was used, with the sole exception that the reaction temperature was changed to 120°C. The result is that the ethylene carbonate conversion was 50.1%, the dimethyl carbonate selectivity was 95.6%, and the ethylene glycol selectivity was 94.5%. Example 24

[0091] The same procedure as in Example 12 was used, with the sole exception that the reaction temperature was changed to 140°C. The result is that the ethylene carbonate conversion was 53.5%, the dimethyl carbonate selectivity was 92.5%, and the ethylene glycol selectivity was 91.9%. Example 25

[0092] The same procedure as in Example 12 was used, with the sole exception that the reaction temperature was changed to 80°C. The result is that the ethylene carbonate conversion was 25.6%, the dimethyl carbonate selectivity was 98.5%, and the ethylene glycol selectivity was 99.1%. Example 26

[0093] The same procedure as in Example 12 was followed, with the only exception that the amount of methanol used was changed to 48 g (the molar ratio of methanol to ethylene carbonate was 6:1). The result was that the ethylene carbonate conversion was 50.5%, the dimethyl carbonate selectivity was 97.1%, and the ethylene glycol selectivity was 96.5%. Example 27

[0094] The same procedure as in Example 12 was followed, with the only exception that the amount of methanol used was changed to 16.0 g (the molar ratio of methanol to ethylene carbonate was 2:1). The result was that the ethylene carbonate conversion was 32.1%, the dimethyl carbonate selectivity was 96.7%, and the ethylene glycol selectivity was 97.1%. Example 28

[0095] The same procedure as in Example 12 was used, with the only exception that the amount of supported quaternary phosphonium catalyst used was changed to 0.55 g (the weight ratio of supported quaternary phosphonium catalyst to ethylene carbonate was 0.025:1). The result was that the ethylene carbonate conversion was 35.1%, the dimethyl carbonate selectivity was 97.1%, and the ethylene glycol selectivity was 96.8%. Example 29

[0096] The same procedure as in Example 12 was used, with the only exception that the amount of supported quaternary phosphonium catalyst used was changed to 2.2 g (the weight ratio of supported quaternary phosphonium catalyst to ethylene carbonate was 0.1:1). The result was that the ethylene carbonate conversion was 51.1%, the dimethyl carbonate selectivity was 93.4%, and the ethylene glycol selectivity was 92.2%. Example 30

[0097] The same procedure as in Example 12 was followed, with the only exception that the amount of supported quaternary phosphonium catalyst used was changed to 4.4 g (the weight ratio of supported quaternary phosphonium catalyst to ethylene carbonate was 0.2:1). The result was that the ethylene carbonate conversion was 52.3%, the dimethyl carbonate selectivity was 93.2%, and the ethylene glycol selectivity was 92.8%. Example 31

[0098] Example 12 was repeated 12 times, with the only exception that from the second time, a spent catalyst resulting from the previous time was used as the supported quaternary phosphonium catalyst, and the results are shown in Table 3. As can be seen from Table 3, the catalyst activity (expressed as ethylene carbonate conversion) decreases to less than 5% after the supported quaternary phosphonium catalyst according to this invention was recycled 12 times. Table 3 Number of recycling processes Ethylene carbonate conversion % Dimethyl carbonate selectivity % Ethylene glycol selectivity % 1 49,2 98,9 98,7 2 49,0 98,5 98,6 3 48,6 99,0 98,5 4 49,0 98,1 99,0 5 48,5 99,1 98,5 6 48,6 99,2 99,0 7 48,4 99,1 98,7 8 48,2 98,9 98,8 9 48,1 98,4 98,5 10 47,8 99,2 98,8 11 48,0 99,1 98,5 12 47,5 99,0 98,4 Example 32

[0099] 10.0 g of support (SG-5 polyvinyl chloride with a K value of 68 to 66 and an average degree of polymerization of 1135-981, produced by Aladdin Reagents (Shanghai) Co., Ltd.) was placed in a 500 mL three-necked flask containing a solution of 2.0 g of triphenylphosphine in 100 mL of benzonitrile, was filtered after reaction for 40 hours at 190°C, washed with ethanol or acetone three times, and vacuum dried at 60°C for 12 hours, and a supported quaternary phosphonium catalyst was obtained.

[0100] 22.0 g of ethylene carbonate, 32.0 g of methanol, and 1.1 g of the supported quaternary phosphonium catalyst were placed in a 100 mL autoclave (with a molar ratio of methanol to ethylene carbonate of 4:1 and a weight ratio of the supported quaternary phosphonium catalyst to ethylene carbonate of 0.05:1) and reacted at 100°C for 4 h. Upon completion of the reaction, the autoclave was cooled to room temperature and evacuated. A sample of the liquid phase was taken and subjected to gas chromatography analysis. The results showed that the ethylene carbonate conversion was 25.1%, the dimethyl carbonate selectivity was 98.2%, the ethylene glycol selectivity was 98.5%, and the elution loss D (%) was 0.5%. Example 33

[0101] 10.0 g of support (chloromethylated cross-linked polystyrene resin, with a Cl content of 19.2 wt% and a cross-linking degree of 5.8%, produced by Jiangsu Suqing Water Treatment Engineering Group Co., Ltd.) was placed in a 500 mL three-necked flask containing a solution of 2.0 g of triphenylphosphine in 100 mL of benzonitrile, was filtered after reaction for 40 hours at 190°C, washed with ethanol or acetone three times, and vacuum dried at 60°C for 12 hours, and a supported quaternary phosphonium catalyst was obtained.

[0102] 22.0 g of ethylene carbonate, 32.0 g of methanol, and 1.1 g of the supported quaternary phosphonium catalyst were placed in a 100 mL autoclave (with a molar ratio of methanol to ethylene carbonate of 4:1 and a weight ratio of the supported quaternary phosphonium catalyst to ethylene carbonate of 0.05:1) and reacted at 100°C for 4 h. Upon completion of the reaction, the autoclave was cooled to room temperature and evacuated. A sample of the liquid phase was taken and subjected to gas chromatography analysis. The results showed that the ethylene carbonate conversion was 39.1%, the dimethyl carbonate selectivity was 98.5%, the ethylene glycol selectivity was 98.3%, and the elution loss D (%) was 0.4%. Example 34

[0103] 10.0 g of carrier (Montmorillonite K-10, produced by J&K Scientific Ltd., with a specific surface area of ​​242 m 2 / g) were placed in a 500 ml three-necked flask, and then 200 ml of anhydrous toluene and 2.0 g of γ-chloropropyltriethoxysilane (CPTES with a molecular structure of C3H6ClSi(OC2H5)3) were added, filtered after refluxing at 100°C for 24 hours, washed with anhydrous ethanol 3 times, and then oven-dried at 110°C for 12 h to obtain a macromolecular agent.

[0104] Then, the obtained macromolecular agent was added to a solution of 2.0 g of triphenylphosphine in 100 ml of benzonitrile, filtered after reaction at 190°C for 40 hours, washed with ethanol and acetone three times, and vacuum dried at 60°C for 12 hours, and a supported quaternary phosphonium catalyst was obtained.

[0105] 22.0 g of ethylene carbonate, 32.0 g of methanol, and 1.1 g of the supported quaternary phosphonium catalyst were placed in a 100 mL autoclave (with a molar ratio of methanol to ethylene carbonate of 4:1 and a weight ratio of the supported quaternary phosphonium catalyst to ethylene carbonate of 0.05:1) and reacted at 100°C for 4 h. Upon completion of the reaction, the autoclave was cooled to room temperature and evacuated. A sample of the liquid phase was taken and subjected to gas chromatography analysis. The results showed that the ethylene carbonate conversion was 18.7%, the dimethyl carbonate selectivity was 86.9%, the ethylene glycol selectivity was 94.2%, and the elution loss D (%) was 0.8%. Example 35 (comparison example)

[0106] 10.0 g of carrier (Montmorillonite K-10, produced by J&K Scientific Ltd. with a specific surface area of ​​242 m 2 / g) were dispersed in a solution of 3.0 g of methyltriphenylphosphine chloride in 100 ml of water. After stirring at 80°C until dry, the resulting mixture was vacuum-dried at 100°C to obtain a catalyst. 22.0 g of ethylene carbonate, 32.0 g of methanol, and 1.1 g of the catalyst were placed in a 100 ml autoclave (with a molar ratio of methanol to ethylene carbonate of 4:1 and a weight ratio of catalyst to ethylene carbonate of 0.05:1) and reacted for 4 h at 100°C. Upon completion of the reaction, the autoclave was cooled to room temperature and evacuated. A sample of the liquid phase was taken and subjected to gas chromatography analysis. The result is that the ethylene carbonate conversion was 25.4%, the dimethyl carbonate selectivity was 95.6%, the ethylene glycol selectivity was 94.8%, and the elution loss D (%) was 25%. Example 36

[0107] 25.7 g of propylene carbonate, 32.0 g of methanol, and 1.1 g of the supported quaternary phosphonium catalyst prepared by Example 1 were placed in a 100 ml autoclave (with a molar ratio of methanol to propylene carbonate of 4:1 and a weight ratio of the supported quaternary phosphonium catalyst to propylene carbonate of 0.05:1) and reacted at 100°C for 4 h. Upon completion of the reaction, the autoclave was cooled to room temperature and evacuated. A sample of the liquid phase was taken and subjected to gas chromatography analysis. The results showed that the ethylene carbonate conversion was 18.7%, the propylene carbonate conversion was 45.2%, the dimethyl carbonate selectivity was 98.9%, and the propylene glycol selectivity was 98.8%. Example 37

[0108] 10.0 g carrier (Aerisol 200, produced by Degussa, with a specific surface area of ​​210 m 2 / g) were placed in a 500 ml three-necked flask, and then 200 ml of anhydrous toluene and 2.0 g of γ-chloropropyltriethoxysilane (CPTES, with a molecular structure of C3H6ClSi(OC2H5)3) were added, and after refluxing at 110°C for 24 hours, filtered, washed with anhydrous ethanol 3 times, and then oven-dried at 110°C for 12 h to obtain a macromolecular agent.

[0109] Then, the obtained macromolecular agent was added to a solution of 2.0 g of 2-di-t-butylphosphine-2',4',6'-triisopropylbiphenyl (CAS No.: 564483-19-8) in 100 ml of benzonitrile, and after reacting at 190°C for 40 hours, the solution was filtered, washed with ethanol and acetone three times, and dried at 60°C for 12 hours in vacuum. A supported quaternary phosphonium catalyst was obtained. 22.0 g of ethylene carbonate, 32.0 g of methanol, and 1.1 g of the supported quaternary phosphonium catalyst were added to a 100 ml autoclave (with a molar ratio of methanol to ethylene carbonate of 4:1 and a weight ratio of the supported quaternary phosphonium catalyst to ethylene carbonate). of 0.05:1) and reacted for 4 hours at 100°C. Upon completion of the reaction, the autoclave was cooled to room temperature and evacuated. A sample was taken from the liquid phase and subjected to gas chromatography analysis.The result is that the ethylene carbonate conversion was 36.4%, the dimethyl carbonate selectivity was 97.4%, the ethylene glycol selectivity was 98.4% and the elution loss D (%) was 0.4%. Example 38

[0110] 10.0 g carrier (Aerisol 200, produced by Degussa, with a specific surface area of ​​210 m 2 / g) were placed in a 500 ml three-necked flask, and then 200 ml of anhydrous toluene and 2.0 g of γ-chloropropyltriethoxysilane (CPTES, with a molecular structure of C3H6ClSi(OC2H5)3) were added, and after refluxing at 110°C for 24 hours, filtered, washed with anhydrous ethanol 3 times, and then oven-dried at 110°C for 12 h to obtain a macromolecular agent.

[0111] Then, the obtained macromolecular agent was added to a solution of 2.0 g of triallylphosphine (CAS No.: 16523-89-0) in 100 ml of benzonitrile, and after reacting at 190°C for 40 hours, the solution was filtered, washed with ethanol and acetone three times, and dried at 60°C for 12 hours in vacuum. A supported quaternary phosphonium catalyst was obtained. 22.0 g of ethylene carbonate, 32.0 g of methanol, and 1.1 g of the supported quaternary phosphonium catalyst were added to a 100 ml autoclave (with a molar ratio of methanol to ethylene carbonate of 4:1 and a weight ratio of the supported quaternary phosphonium catalyst to ethylene carbonate of 0.05:1) and dried at 100°C for 4 hours. reacted. Upon completion of the reaction, the autoclave was cooled to room temperature and evacuated. A sample of the liquid phase was taken and subjected to gas chromatography analysis.The result is that the ethylene carbonate conversion was 36.4%, the dimethyl carbonate selectivity was 97.4%, the ethylene glycol selectivity was 98.4% and the elution loss D (%) was 0.4%.

Claims

[1] A process for producing a supported quaternary phosphonium catalyst comprising a step of reacting a tertiary phosphine represented by the following formula (2) with a macromolecular agent represented by the following formula (3), wherein the weight ratio of the tertiary phosphine to the macromolecular agent is 1 to 20:80 to 99, preferably 1 to 15:85 to 99, wherein R1, R2 and R3 are identical or different from each other and are each independently selected from the group consisting of an optionally substituted straight-chain or branched C 1-20 -alkyl, optionally substituted straight-chain or branched C 2-20 -Alkenyl, optionally substituted straight-chain or branched C 2-20 -alkynyl, optionally substituted C 3-20 -cycloalkyl or optionally substituted C 6-20 -Aryl, preferably straight-chain or branched C 2-10 -Alkyl, straight-chain or branched C 2-10-Alkyl substituted by one or more phenyl or C 3-20 -Cycloalkyl, straight-chain or branched C 2-10 -Alkenyl, straight-chain or branched C 2-10 -Alkenyl, substituted by one or more phenyl or C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl, C 3-20 -Cycloalkyl substituted by one or more straight-chain or branched C 2-6 -Alkyl or straight-chain or branched C 2-6 -Alkenyl, C 6-20 -aryl or C 6-20 -aryl substituted by one or more straight-chain or branched C 1-6 -alkyl or straight-chain or branched C 2-6 -Alkenyl, - is a covalent bond, where X is a halogen atom preferably Cl, Br or I, more preferably Br or I, L is a divalent binding group, preferably selected from the group consisting of optionally substituted straight-chain or branched C 1-20-alkylene, optionally substituted straight-chain or branched C 2-20 -alkenylene or optionally substituted straight-chain or branched C 2-20 -alkynylene, more preferably from the group consisting of a straight-chain or branched C 1-20 -alkylene, more preferably selected from the group consisting of straight-chain C 2-8 -Alkylene, wherein the alkylene, alkenylene or alkynylene is optionally modified by one or more, for example 1 to 3, 1 to 2 or one, intermediate group selected from the group consisting of -O-, -S-, -NR a -, where R a C 1-4 -alkyl, and phenylene, preferably phenylene, is a carrier, preferably one or more selected from the group consisting of an organic carrier and inorganic carrier, more preferably one or more selected from the group consisting of an inorganic carrier, more preferably one or more selected from the group consisting of silica, zeolite, preferably SBA-15, MCM-41, MCF, HMS, KIT-6 or SBA-16, and diatomaceous earth, - is a covalent bond, wherein the reaction temperature is 100 to 190°C and the reaction time is 10 to 40 hours. [2] The process according to claim 1, wherein the reaction temperature is 120 to 190°C and the reaction time is 10 to 30 hours. [3] The method according to claim 1, wherein the support is one or more selected from the group consisting of silica, zeolite, preferably SBA-15, MCM-41, MCF, HMS, KIT-6 or SBA-16, and diatomaceous earth and the macromolecular agent is produced by a reaction between the carrier and a halogenating agent of the following formula (4), wherein the weight ratio of the halogenating agent to the carrier is 0.005 to 0.15:1, preferably 0.01 to 0.1:1, wherein X is a halogen atom, preferably Cl, Br or I, more preferably Cl, L is a divalent binding group, preferably selected from the group consisting of an optionally substituted straight-chain or branched C 1-20 -alkylene, optionally substituted straight-chain or branched C 2-20 -alkenylene or optionally substituted straight-chain or branched C 2-20 -alkynylene, more preferably selected from the group consisting of a straight-chain or branched C 1-20 -alkylene, more preferably selected from the group consisting of a straight-chain C 2-8-Alkylene, wherein the alkylene, alkenylene or alkynylene may optionally contain one or more, for example 1 to 3, 1 to 2 or one, groups selected from the group consisting of -O-, -S-, -NR a -, where R a C 1-4 -alkyl and phenylene, preferably phenylene, M is Ti, Si or Zr, preferably Si, R4, R5 and R6 are identical or different from each other and are each independently selected from the group consisting of straight-chain or branched C 1-4 -Alkoxy, preferably methoxy or ethoxy. [4] The process according to claim 3, wherein in the reaction between the carrier and the halogenating agent, the reaction temperature is 70 to 140°C, preferably 90 to 120°C and the reaction time is 1 to 60 hours, preferably 5 to 48 hours. [5] The process of claim 3, wherein X is Cl and the process further comprises a step of contacting the macromolecular agent with one or more modifying agents selected from the group consisting of a brominating agent, preferably alkali metal bromide, more preferably one or more selected from the group consisting of LiBr, NaBr, KBr and CsBr, and an iodinating agent, preferably alkali metal iodide, more preferably one or more selected from the group consisting of LiI, NaI, KI and CsI, prior to the reaction of the macromolecular agent with the tertiary phosphine, wherein the weight ratio of the modifier to the macromolecular agent is 0.01 to 1:1, preferably 0.02 to 0.6:

1. [6] Use of a supported quaternary phosphonium catalyst produced according to the process according to any one of claims 1 to 5 as a catalyst in the co-production of a di-C 1-10 -alkyl carbonate and a C2-10 -alkanediols by a transesterification process. [7] A process for producing a dialkyl carbonate comprising a step of contacting a C 2-10 -alkylene carbonate, preferably ethylene carbonate or propylene carbonate, with a monovalent C 1-10 -alcohol, preferably methanol, in the presence of a supported quaternary phosphonium catalyst produced according to the process of any one of claims 1 to 5, to produce a di-C 1-10 -alkylcarbonates, preferably dimethyl carbonate, and one C 2-10 -alkanediols, preferably ethylene glycol or propylene glycol. [8] A process according to claim 7, wherein the reaction temperature is 60 to 140°C, preferably 80 to 140°C, the reaction time is 0.1 to 20 hours, preferably 1 to 10 hours, the molar ratio of the monovalent C 1-10 -alkanol to C 2-10-Alkylene carbonate 2 to 10:1, preferably 2 to 6:1 and the weight ratio of the supported quaternary phosphonium catalyst to the C 2-10 -Alkylene carbonate is 0.005 to 0.5:1, preferably 0.01 to 0.2:1.