CN113019460A - Iridium complex catalyst and preparation method thereof - Google Patents

Iridium complex catalyst and preparation method thereof Download PDF

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CN113019460A
CN113019460A CN202011491271.3A CN202011491271A CN113019460A CN 113019460 A CN113019460 A CN 113019460A CN 202011491271 A CN202011491271 A CN 202011491271A CN 113019460 A CN113019460 A CN 113019460A
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iridium
catalyst
vinylpyridine
complex catalyst
methanol
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CN113019460B (en
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张志炳
胡宗贵
张德谨
朱桂生
周政
胡兴邦
赵禄强
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JIANGSU SOPO CHEMICAL CO LTD
Nanjing Institute of Microinterface Technology Co Ltd
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JIANGSU SOPO CHEMICAL CO LTD
Nanjing Institute of Microinterface Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium

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  • Organic Chemistry (AREA)
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Abstract

The invention provides an iridium complex catalyst and a preparation method thereof, wherein the iridium complex catalyst is obtained by taking a copolymer formed by 2-vinylpyridine and vinyl diphenylphosphine as a ligand and carrying out coordination reaction with an iridium compound. The catalyst takes a copolymer formed by 2-vinylpyridine and vinyl diphenylphosphine as a ligand, and the iridium-based catalyst for preparing the methanol carbonylation reaction has better applicability to the current mainstream production process and production device.

Description

Iridium complex catalyst and preparation method thereof
Technical Field
The invention relates to the field of catalyst preparation, and particularly relates to an iridium complex catalyst and a preparation method thereof.
Background
Acetic acid is a very important chemical product, and products derived from the acetic acid are hundreds of types, and are widely applied to medicines, pesticides, foods and other related industries. Currently, methanol carbonylation is the most widely used technical route for producing acetic acid in industry. The catalyst for preparing acetic acid by methanol carbonylation in industry is subject to three stages of cobalt-based catalyst developed by BASF company, rhodium-based catalyst developed by Monsanto company and iridium-based catalyst developed by BP company, wherein the iridium-based catalyst has the characteristics of relatively low price, low water content, high catalytic activity and the like, and has become the mainstream catalyst for producing acetic acid by methanol carbonylation. However, the iridium-based catalyst still has the problems that the reaction system seriously corrodes equipment, and metallic iridium is easy to precipitate and deactivate.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide an iridium complex catalyst, wherein a copolymer formed by two types of 2-vinylpyridine with relatively strong electron donating capability and vinyl diphenylphosphine is used as a ligand, so that the formed catalyst has high activity and excellent catalytic performance.
The second purpose of the invention is to provide a preparation method of the iridium complex catalyst, which has simple operation steps and excellent catalytic effect of the prepared catalyst.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides an iridium complex catalyst which is obtained by taking a copolymer formed by 2-vinylpyridine and vinyl diphenylphosphine as a ligand and carrying out coordination reaction with an iridium compound, wherein the addition amount of iridium is 5-12 wt% of the mass of the copolymer.
The amount of iridium added is calculated as a specific iridium element.
Related researches show that the methanol carbonylation catalyst using the copolymer as the ligand has the advantages of high activity, low equipment corrosion and high stability, and the higher the density of electron cloud on the metal of the catalyst, the higher the catalytic activity of the catalyst. In order to obtain a catalyst with higher activity, the invention designs and synthesizes a copolymer formed by two 2-vinylpyridine with stronger electron donating capability and vinyl diphenylphosphine as a ligand, the active metal iridium and N on the 2-vinylpyridine with stronger electron donating capability and P on the vinyl diphenylphosphine are subjected to coordination reaction, the electron cloud density on the active metal iridium is increased, the catalytic activity of the iridium-based catalyst is improved, and particularly in the process of producing acetic acid by methanol carbonylation reaction, the invention can ensure that the reaction pressure for producing acetic acid by methanol carbonylation reaction is reduced to about 2MPa and the conversion rate of methanol can be maintained to more than 97 percent under the condition that the reaction pressure is lower than that of the traditional reaction pressure, even up to 99%.
The reason why the ratio of iridium to copolymer needs to be controlled in the present invention is that iridium is used as the active center of the whole catalytic system, and too little addition will affect the catalytic activity, while too much addition may result in part of iridium not being coordinated with the copolymer ligand, while the uncoordinated metallic iridium not only has low catalytic activity but also is difficult to recover, and may even affect the selectivity of the reaction.
Preferably, in order to improve the catalytic activity of the catalyst, the molar ratio of the 2-vinylpyridine to the vinyldiphenylphosphine is (5-7): (3-5), the reason is that the monomer polymerization process is a polymerization reaction initiated by free radicals, so that two coordination units of N → Ir and P → Ir with different strengths exist in the catalyst structure, and N and P can be coordinated with Ir into a main coordination form simultaneously by regulating and controlling the polymerization conditions. Thus, on the one hand, the catalyst body can be in a stable state by utilizing the strong coordination between N and Ir, and on the other hand, the relatively weak P → Ir coordination bond is easy to dissociate, which is beneficial to the oxidative addition reaction of methyl iodide, and the step is also a control step of the methanol carbonylation reaction process, so that the purpose of controlling the polymerization reaction can be achieved only by controlling the ratio of two monomers, which is also obtained by a large amount of practice.
Preferably, the catalyst also comprises a promoter ruthenium compound, wherein the molar ratio of the ruthenium element to the iridium element is (4-6): 1.
Preferably, the type of the ruthenium compound promoter is Ru (CO)4I2、RuCl3、[Ru(CO)4I2]2Any one or a mixture of several of them;
preferably, the iridium compound is of the type IrCl3、[Ir(CO)2I]2、[Ir(CO)2Cl]2Or Ir (OAc)3Any one or a mixture of several of them.
The catalyst obtained by matching the iridium catalyst with the copolymer has better catalytic activity than the conventional iridium-based catalyst, and particularly can remarkably improve the conversion rate of raw materials and the yield of products in the production of acetic acid by methanol carbonylation reaction. In a relatively large way, the influence on the electron density of metal after coordination is large in the aspect of a coordination mechanism of the conventional copolymer ligand, and the catalytic effect of the iridium metal is finally and directly influenced, so that the inventors find that the catalytic effect of the catalyst can be remarkably improved by adopting the specific polymer of the invention after a plurality of practices.
The invention also provides a preparation method of the iridium complex catalyst, besides providing the formula of the catalyst, which comprises the following steps:
carrying out polymerization reaction on 2-vinylpyridine, vinyl diphenylphosphine, a solvent and an initiator to obtain a copolymer ligand;
and stirring and mixing the copolymer ligand, the ruthenium compound and the promoter.
Preferably, the polymerization temperature is 60-70 ℃ and the polymerization time is 8-12 h.
Preferably, the addition amount of the initiator is 1-3 wt% of the mass of the 2-vinylpyridine and the vinyl diphenylphosphine.
Preferably, the time for mixing with stirring is 30-60 min.
Preferably, the solvent is one of benzene and toluene.
Preferably, the initiator is dibenzoyl peroxide.
By regulating and controlling each parameter in the preparation method in a proper range, the performance of the prepared catalyst can be obviously improved.
In a word, the catalyst obtained by the preparation method can be better applied to the process of producing acetic acid by methanol carbonylation catalytic reaction, and has better applicability to the existing mainstream production process and production device.
In the reaction catalysis process, the addition amount of the iridium-based catalyst is 500-5000 ppm calculated by iridium, the mass fraction of water in the whole reaction system is 5%, the mass fraction of methyl iodide in the whole reaction system is 6%, the CO pressure is 1.5-2MPa, and the reaction temperature is 170-220 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the catalyst of the invention selects a copolymer formed by two 2-vinylpyridine with stronger electron donating capability and vinyl diphenylphosphine as a ligand, and an iridium complex catalytic system for preparing acetic acid by high-activity methanol carbonylation is formed by coordination of the novel ligand and metal iridium;
(2) the iridium catalyst preparation method provided by the invention is simple in operation steps, and the prepared catalyst is excellent in catalytic effect;
(3) the catalyst forms a metal complex with a stable structure after being coordinated with the metal iridium, and compared with a common methanol carbonylation reaction catalyst, a heterogeneous catalysis system formed by the catalyst has higher activity, so that the methanol carbonylation reaction can be carried out at relatively lower temperature and pressure. Meanwhile, the catalyst is heterogeneous, so that the catalyst is easier to recover.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a gas chromatogram of the product provided in example 3 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The reaction process of catalyst preparation and methanol carbonylation to prepare acetic acid comprises the following steps:
(1) accurately measuring 0.01mol of 2-vinylpyridine and 0.01mol of vinyl diphenylphosphine, adding 0.06g of dibenzoyl peroxide and 24mL of toluene solvent, and reacting at 65 ℃ for 12h to obtain a copolymer ligand. And then 0.5g of copolymer ligand is weighed and dissolved in methanol, iridium chloride accounting for 10 wt% of the total mass of the 2-vinylpyridine and the vinyl diphenylphosphine is added into the solution, the solution is stirred for 30min at room temperature, and then the solution is precipitated by diethyl ether, washed and dried to obtain the iridium-based catalyst.
(2) Weighing 0.1g of iridium-based catalyst, placing the iridium-based catalyst into a high-pressure reaction kettle, adding 0.2g of ruthenium chloride hydrate into the reaction kettle, stirring for 5min to obtain an iridium complex catalyst, adding 10mL of methanol, 0.2mL of methyl iodide and 3mL of water, introducing CO to enable the pressure in a reaction system to be 1.5MPa, and reacting for 12h at the temperature of 180 ℃, wherein the conversion rate of methanol is 97%.
Example 2
The reaction process of catalyst preparation and methanol carbonylation to prepare acetic acid comprises the following steps:
(1) accurately measuring 0.015mol of 2-vinylpyridine and 0.01mol of vinyl diphenylphosphine, adding 0.07g of dibenzoyl peroxide and 28mL of toluene solvent, and reacting at 60 ℃ for 8h to obtain a copolymer ligand. And then 0.5g of copolymer ligand is weighed and dissolved in methanol, iridium chloride accounting for 10 wt% of the total mass of the 2-vinylpyridine and the vinyl diphenylphosphine is added into the solution, the solution is stirred for 30min at room temperature, and then the solution is precipitated by diethyl ether, washed and dried to obtain the iridium-based catalyst.
(2) Weighing 0.1g of iridium-based catalyst, placing the iridium-based catalyst in a high-pressure reaction kettle, adding 0.2g of ruthenium chloride hydrate, stirring for 10min to obtain an iridium complex catalyst, adding 10mL of methanol, 0.2mL of methyl iodide and 3mL of water, introducing CO to ensure that the pressure in a reaction system is 1.5MPa, and reacting for 12h at the temperature of 180 ℃, wherein the conversion rate of methanol is 97%.
Example 3
The reaction process of catalyst preparation and methanol carbonylation to prepare acetic acid comprises the following steps:
(1) accurately measuring 0.02mol of 2-vinylpyridine and 0.01mol of vinyl diphenylphosphine, adding 0.086g of dibenzoyl peroxide and 34mL of toluene solvent, and reacting at 70 ℃ for 10h to obtain a copolymer ligand. And then 0.5g of copolymer ligand is weighed and dissolved in methanol, iridium chloride accounting for 10 wt% of the total mass of the 2-vinylpyridine and the vinyl diphenylphosphine is added into the solution, the solution is stirred for 30min at room temperature, and then the solution is precipitated by diethyl ether, washed and dried to obtain the iridium-based catalyst.
(2) Weighing 0.1g of iridium-based catalyst, placing the iridium-based catalyst in a high-pressure reaction kettle, adding 0.2g of ruthenium chloride hydrate into the reaction kettle, stirring the mixture for 30min to obtain an iridium complex catalyst, adding 10mL of methanol, 0.2mL of methyl iodide and 3mL of water, introducing CO to enable the pressure in a reaction system to be 1.5MPa, reacting the mixture for 12h at the temperature of 180 ℃, wherein the conversion rate of methanol is 98%, and specific results can be shown in a gas chromatogram of FIG. 1.
Example 4
0.1g of the intermediate catalyst obtained in example 3 was weighed and placed in an autoclave, 0.2g of ruthenium chloride hydrate was added thereto to obtain an iridium complex catalyst, 10mL of methanol, 0.2mL of methyl iodide and 3mL of water were added thereto, 2MPa of CO gas was introduced thereto, and the reaction was carried out at 180 ℃ for 24 hours with a methanol conversion of 99%.
Example 5
0.1g of the catalyst obtained in example 3 was weighed and placed in an autoclave, 0.2g of ruthenium chloride hydrate was added thereto to obtain an iridium complex catalyst, 10mL of methanol, 0.2mL of methyl iodide and 3mL of water were added thereto, and 2MPa of CO gas was introduced and reacted at 170 ℃ for 12 hours with a methanol conversion of 97%.
Example 6
0.1g of the catalyst obtained in example 3 was weighed and placed in an autoclave, 0.2g of ruthenium acetate was added thereto to obtain an iridium complex catalyst, 10mL of methanol, 0.2mL of methyl iodide and 3mL of water were added thereto, 2MPa of CO gas was introduced thereto, and the mixture was reacted at 180 ℃ for 24 hours with a methanol conversion of 99%.
Example 7
The other procedure was identical to example 3, except that the molar ratio of 2-vinylpyridine to vinyldiphenylphosphine was 5:3, and the conversion of methanol was determined to be 97%.
Example 8
The other procedure was identical to example 3, except that the molar ratio of 2-vinylpyridine to vinyldiphenylphosphine was 7:5, and the conversion of methanol was determined to be 98%.
Example 9
The other procedure was identical to example 3, except that the molar ratio of 2-vinylpyridine to vinyldiphenylphosphine was 8:1, and the conversion of methanol was determined to be 80%.
Example 10
The other procedure was in accordance with example 3, except that the molar ratio of the ruthenium element in the hydrous ruthenium oxide to the iridium element in the iridium-based catalyst was 4:1, and the conversion of methanol was determined to be 97%.
Example 11
The other procedure was in accordance with example 3, except that the molar ratio of the ruthenium element in the hydrous ruthenium oxide to the iridium element in the iridium-based catalyst was 6:1, and the conversion of methanol was determined to be 99%.
Example 12
The other procedure was in accordance with example 3, except that the molar ratio of the ruthenium element in the hydrous ruthenium oxide to the iridium element in the iridium-based catalyst was 5:1, and the conversion of methanol was determined to be 99%.
Example 13
The further procedure was in accordance with example 3, the iridium chloride addition ratio being adjusted to 5% by weight, and the conversion of methanol being determined to be 97%.
Example 14
The further procedure was in accordance with example 3, the iridium chloride addition ratio being adjusted to 12% by weight, and the conversion of methanol being determined to be 98%.
Comparative example 1
The process was carried out according to example 4 of patent CN101693209A, the conversion of methanol being 94%.
Comparative example 2
The specific procedure is in accordance with example 3, except that vinyldiphenylphosphine is replaced by methyl acrylate and the final methanol conversion is determined to be 80%, probably because the conversion is reduced more because the pressure is too low, which has an effect on the catalytic activity of the catalyst.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. An iridium complex catalyst is characterized by being obtained by taking a copolymer formed by 2-vinylpyridine and vinyl diphenylphosphine as a ligand and carrying out coordination reaction with an iridium compound, wherein the addition amount of iridium is 5-12 wt% of the mass of the copolymer.
2. The iridium complex catalyst according to claim 1, wherein the molar ratio of 2-vinylpyridine to vinyldiphenylphosphine is (5-7): (3-5).
3. The iridium complex catalyst according to claim 1, further comprising a promoter ruthenium compound, wherein a molar ratio of the ruthenium element to the iridium element is (4-6): 1.
4. The iridium complex catalyst according to claim 1, wherein the promoter ruthenium compound is of the type Ru (CO)4I2、RuCl3、[Ru(CO)4I2]2Any one or a mixture of several of them;
preferably, the iridium compound is of the type IrCl3、[Ir(CO)2I]2、[Ir(CO)2Cl]2Or Ir (OAc)3Any one or a mixture of several of them.
5. The process for producing an iridium complex catalyst according to any one of claims 1 to 4, comprising the steps of:
carrying out polymerization reaction on 2-vinylpyridine, vinyl diphenylphosphine, a solvent and an initiator to obtain a copolymer ligand;
and stirring and mixing the copolymer ligand, the iridium compound and the accelerator.
6. The process according to claim 5, wherein the polymerization temperature is 60 to 70 ℃ and the polymerization time is 8 to 12 hours.
7. The process according to claim 5, wherein the initiator is added in an amount of 1 to 3 wt% based on the total mass of the 2-vinylpyridine and the vinyldiphenylphosphine.
8. The method according to claim 5, wherein the time for mixing with stirring is 30 to 60 min.
9. The method according to claim 5, wherein the solvent is one of benzene and toluene.
10. The method of claim 5, wherein the initiator is dibenzoyl peroxide.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4358411A (en) * 1979-06-29 1982-11-09 The Halcon Sd Group, Inc. Preparation of carbonylation products
US4996178A (en) * 1987-02-05 1991-02-26 The Goodyear Tire & Rubber Co. Low temperature synthesis of condensation polymers
US5731255A (en) * 1994-07-22 1998-03-24 Daicel Chemical Industries, Ltd. Catalytic systems and methods for carbonylation
CN101693209A (en) * 2009-08-24 2010-04-14 江苏索普（集团）有限公司 Iridium picolinate complex catalyst for synthesizing acetic acid by methanol carbonylation
CN102489327A (en) * 2011-11-24 2012-06-13 重庆大学 Catalyst for acetic acid synthesis through methanol carbonylation and its application method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4358411A (en) * 1979-06-29 1982-11-09 The Halcon Sd Group, Inc. Preparation of carbonylation products
US4996178A (en) * 1987-02-05 1991-02-26 The Goodyear Tire & Rubber Co. Low temperature synthesis of condensation polymers
US5731255A (en) * 1994-07-22 1998-03-24 Daicel Chemical Industries, Ltd. Catalytic systems and methods for carbonylation
CN101693209A (en) * 2009-08-24 2010-04-14 江苏索普（集团）有限公司 Iridium picolinate complex catalyst for synthesizing acetic acid by methanol carbonylation
CN102489327A (en) * 2011-11-24 2012-06-13 重庆大学 Catalyst for acetic acid synthesis through methanol carbonylation and its application method

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