CN1047329C - Multi dentate heterodesmic Rh catalyst and its prepn. method - Google Patents

Abstract

The present invention relates to a catalyst formed by multitooth mixed bonding type organic and high-molecular ligand bound transitional metal rhodium species. The reaction temperature and the pressure condition are relevant moderate when a methoxy compound and carbon monoxide are used for preparing acetic acid, methyl acetate and acetic anhydride. Because the multitooth ligand in the catalyst can be simultaneously bound with the center of rhodium (1) ions in various bonding forms such as ion pairs, coordination complexation, etc., the formed organic and high-molecular multitooth mixed bonding type rhodium (1)ionic complex catalyst is stable in a carbonylation reaction system, and has high catalytic activity and selectivity.

Description

Multiple tooth heterodesmic mould assembly rhodium catalyst and method for making and purposes

The invention belongs to organic and macromolecule-metal complex carbonylating catalyst.

Carbon monoxide (CO) under catalyst action, with methyl alcohol reaction system acetate, with methyl acetate reaction system acetic anhydride, this is the organic acid that grows up in the 40-50 age in this century and the novel method for synthesizing of acid anhydrides, it is synthetic to be called carbonyl.At the beginning of the seventies, people such as Meng Shandou (Monsanto) Paulik of company are about the invention (US3769329,1972) of rhodium catalyst, for the carbonyl synthesizes industrialization has been opened up new enforcement approach.Over nearly more than 20 years, this respect has a large amount of reaction mechanisms, new catalyst system and the improved research of technology thereof to report.

Methoxylation compound in the solution is realized carbonylation with carbon monoxide under rhodium catalyst (cat.) effect, particularly iodomethane is to this reactions steps of oxidation addition of catalytic active species need to pass through co-catalyst halide one, and elder generation generates acetyl iodide: Acetyl iodide than be easier to reaction system in first alcohol and water etc. continue reaction, generate acetate and methyl acetate, regeneration iodomethane or hydrogen iodide simultaneously, the latter is converted to iodomethane again in reaction system, finish catalytic cycle and utilized again.If preparation is acetic anhydride, above methyl alcohol is replaced by methyl acetate or dimethyl ether.Just methyl acetate or reactions such as dimethyl ether and acetyl iodide are not carried out so easily, need in reaction system they be transformed into acetate earlier, and reaction could be finished smoothly:

(2) in the homogeneous carbonylation reaction system of Meng Shandou, dicarbapentaborane diiodo-rhodium (I) anion was acknowledged as the catalytic active species of carbonylation in the past.For making it in reaction medium, be easy to form, in reaction system, add the organic matter part of nitrogenous, phosphorus, arsenic, antimony usually, with formation dicarbapentaborane diiodo-rhodium (I) ionic complex [Rh (CO) ₂I ₂] ^-+QR ₄(Q=nitrogen group element, i.e. N, P, As, Sb; The R=alkyl, aryl).But this class rhodium compound very easily becomes trivalent rhodium precipitation in the running use, cause catalyst activity to reduce even inactivation, has increased the reclaiming expense of catalyst.In actual production process,, except that guaranteeing enough CO dividing potential drops, also take to add the way of big water gaging and hydrogen iodide usually, to guarantee the stable existence of rhodium (I) catalyst in order to help improving or to keep catalytic activity, prevent the catalysqt deactivation precipitation.But so, not only reaction medium is more serious to the corrosion phenomenon of production equipment, and water content increases in the thick acid that steams at first, also has water-hydroiodic acid azeotropic mixture and occurs, and product separates more complicated, and energy consumption significantly rises.In fact, it also is limited doing actual effect like this.Also have the reason of following two main aspects because cause catalysqt deactivation: the first adopts the high temperature flash process to make in product and the catalyst separation process, because of losing in the protection of reducing gases atmosphere or the catalyst system effusion of easily cracking and volatile component, thereby cause metallic catalyst inactivation precipitation; Then be because high temperature in the carbonylation processes and the improper institute of reaction system composition control cause on the other hand.For reaching sufficiently high rate of catalysis reaction and increasing sensible heat, be beneficial to flash process, the reaction temperatures for carbonylation will in the current methods will remain on more than 180 ℃, and this stability to above-mentioned rhodium (I) compound is totally unfavorable.

People such as Drago [Inorg.Chem, 20 (1981) 641-644; US4328125] find that anion exchange resin can form stable rhodium (I) complex with dicarbapentaborane diiodo-rhodium (I) anion, and can be used to carry out heterogeneous methanol carbonylation, its catalytic activity and homogeneous catalyst suitable.Just the reaction temperature that is adopted is 120-130 ℃, fails to give full play to the usefulness of catalyst.Employed in addition reaction pressure 0.4-1.1MPa for CO dividing potential drop lower range district, causes the experimental result of its catalytic rate and space-time yield very poor, does not have industrial using value to say.The two coordination bonding rhodiums of macromolecule ligand that had document and patent to use phosphorous or nitrogen, oxygen difunctional respectively afterwards form suitable-dicarbapentaborane rhodium cation the macromolecule rhodium catalyst, carry out the carbonylation experiment, actual effect is all less than homogeneous catalyst, its overall catalytic activity only reaches the latter's 60-70%[KI SU RO et.al., J.Mol.Catal., 59 (1990) 353-366; J.Hjortkjaer et.al., Appl.Catal., 67 (1991) 269-278].

The purpose of this invention is to provide a kind of multiple tooth heterodesmic mould assembly rhodium catalyst and method for making and purposes, by changing the part The Nomenclature Composition and Structure of Complexes of methoxylation compound carbonylating catalyst and active specy thereof, to improve the chemical compatibility between each part in the reaction system, improve the stability and the catalytic activity of catalyst, under gentle relatively reaction condition, realize the carbonylation method production of acetate, methyl acetate and acetic anhydride, and cut down the consumption of energy and the reclaiming expense of catalyst.

Research is pointed out, in the methoxycarbonyl process, along with the difference of employed catalyst The Nomenclature Composition and Structure of Complexes and reaction system, exists multiple possible mechanism of catalytic reaction and catalytic active species thereof.Find that so far with dicarbapentaborane diiodo-rhodium (I) anion be the carbonylation process of catalytic active species, on reaction speed, more take advantage, especially be in (C.E.Hickey et al. under the environment that might form the asymmetrical pentacoordinate species that nucleophilicity is stronger, activity is higher at them, J.Chem.Soc., Chem.Commun., (1984) 1609; M.Murphy et al., J.Organomet.Chem., 303 (1986) 257).Just this class pentacoordinate species life-span extremely short, also do not have the instrument means so far and can be used to directly prove its existence.For verifying catalyst that the people proposed and phosphorous or nitrogen such as aforementioned Drago, the two differences of coordination high polymer rhodium catalyst on catalytic activity of oxygen difunctional, in example 2 of the present invention and 17, we have adopted the degree of cross linking of different quaternization degrees to be 15% 2-vinylpyridine/divinylbenzene copolymer (PVPy215) and 4-vinylpyridine/divinylbenzene copolymer (PVPy415) and have made part, the macromolecule rhodium catalyst (PVPy215/Rh and PVPy415/Rh) that the bonding rhodium forms has carried out the catalytic reaction experiment of carbonylation of methanol and methyl acetate carbonylation respectively, the result is shown in Fig. 1-2

Fig. 1 .PVPy215/Rh in methanol carbonylation catalytic rate with the variation of quaternized degree

Fig. 2 .PVPy415/Rh in the methyl acetate carbonylation catalytic rate with the variation of quaternized degree as seen, carbonylation rate of catalysis reaction (TON) all significantly improves with the part of catalyst is quaternized, but is not to be that quaternization degree is high more good more.This experimental fact and the present invention resulting result in example 4-8 and 13-16 shows, why this class catalyst shows high catalytic activity, be because wherein contained part or all of nitrogen, phosphorus by the quaternary salt change multiple tooth heterodesmic mould assembly part and dicarbapentaborane diiodo-rhodium (I) anion [Rh (CO) ₂I ₂] ^-Formation has rhodium (I) ionic complex of (A) shown in the back or (A ') architectural feature.In such class compound catalyst that organic or macromolecule ligand and rhodium form by the multiple tooth heterodesmic mould assembly of nitrogenous, phosphorus, oxygen, sulphur, quaternary salt ion (L ⁺) and two kinds of part unit of free base (L °) simultaneously and deposit and interconnect, they with ion pair, again can ligand complex etc. heterodesmic close form and rhodium (I) ions binding.Owing to have the rhodium activated centre that is in the coordination undersaturated condition in lonely dicarbapentaborane diiodo-rhodium (I) anion of part unit (L °) in the part, have to the effect of electronics ligand complex to the square plane configuration of stable symmetry to free electron, thereby form very unstable but active higher pentacoordinate catalytic active species (A), consequently brought out the oxidation addition of halide, particularly iodomethane, promoted the carrying out of carbonylation the rhodium catalytic activity species.And the rate controlling step that this oxidation addition reaction is whole carbonylation catalytic reaction process.

Based on above-mentioned experiment discovery and inventive concept, the present invention succeeds in developing a series of catalysis methoxylation compounds that are used for and carries out novel homogeneous phase and the heterogeneous catalyst that carbonylation is produced acetate, methyl acetate and acetic anhydride.Technology of the present invention constitutes, and mainly comprises the multiple tooth organic and macromolecule ligand with certain architectural feature, and rhodium (I) the ionic complex catalyst and the method for making thereof of preparation thus.

Multiple tooth heterodesmic mould assembly rhodium catalyst of the present invention is characterized in that: (1) is formed, is had (A) or (A ') by multiple tooth heterodesmic mould assembly part and dicarbapentaborane diiodo-rhodium (I) anion

The rhodium of architectural feature (I) ionic complex catalyst, this is that a class is with quaternary salt ion (L ⁺) and two kinds of part unit forms of free base (L °) and depositing and the multiple tooth organic or macromolecule ligand of interconnective nitrogenous, phosphorus, oxygen, sulphur, with ion pair, simultaneously again can ligand complex etc. heterodesmic close the compound of form bonding rhodium; (2) in molecular skeleton, main chain, side chain or the side group of the organic or macromolecule ligand of multiple tooth heterodesmic mould assembly, must contain two or more nitrogen, phosphorus, oxygen, sulphur functional group, wherein have a nitrogenous or phosphorus at least, and by quaternary saltization.With L ° (N, P, O, S) or be abbreviated as L ° represent one can be to the functional group or the part unit of nitrogenous, the phosphorus that is in free state of the empty d track contribution lone pair electrons of transition metal, oxygen, sulphur.At L ° or following L ⁺The back is added with normally specific functional element or the group in order to indicate that especially this part unit is contained of parantheses.L ° (N, P) by after the quaternary saltization with L ⁺(R) or slightly be written as L ⁺Expression, parenthetic R is the substituting group that quaternary salt reagent place selects for use, is generally alkyl or aryl, the most frequently used is methyl; (3) in same ligand molecular, a plurality of L can be arranged ⁺Exist simultaneously with L ° of part unit, between two part unit of direct neighbor with " " or "～" symbolic representation connection.L ° of adjacent two part unit

L ⁺(or be expressed as L °～L ⁺) between distance can grow without limits, but from the catalytic activity experiment effect, 1-9 the carbon atom of preferably being separated by also might connect on these carbon atoms or alternate hetero atom or other group arranged, its main chain backbone connects with covalent bond, comprises aromatic gp, alicyclic ring key, singly-bound and Multiple Bonds; (4) and L ⁺Directly free base part unit L ° of adjacency is 1 at least, as many as 2-3; Preferably two (L °-L ⁺～L °) or three, that is (L °～) ₃L ⁺From L ° and L ⁺See L ° and L on arranged evenly in the linearity of molecule or three-dimensional structure ⁺Connect and be arranged as the best in alternate mode; (5) set of dispense of catalyst ratio and structure, although wherein the consumption of rhodium might not need strict restriction, but generally the content of rhodium in catalyst should be controlled between the 0.5-25wt%, as with the densimeter of rhodium in carbonylation reaction system, should remain in the 0.1-50mmol/L scope, preferably 1-20mmol/L; Nitrogenous and the phosphorus atoms sum of institute is 2-100 to the ratio of rhodium atom in multidentate ligand, preferably 5-30; The nitrogen, the phosphorus group (L that in multidentate ligand, occur with the quaternary salt ionic species ⁺) with the ratio that has probability of the nitrogen that occurs with free base form, phosphorus, oxygen, methylthio group (L °) be 0.1-3, preferably remain in the 0.2-1 scope.

The multiple tooth organic and macromolecule ligand that can be made with architectural feature of the present invention is a lot, as long as contain two or more nitrogen, phosphorus, oxygen, sulphur functional group or functional unit in these compound molecules, and wherein have at least one to be nitrogen or phosphorus functional group.With regard to organic molecule, but equal quaternary saltization of following three compounds or part quaternary saltization are made the part with said structure feature: (1) contains the fragrant heterocycle and the aliphatic compounds of two or more nitrogen-atoms, for example compound and derivatives thereof such as imidazoles, triazole, tetrazolium, bipyridyl, naphthyridines, pyrimidine, pyrazine, triazine, tetrazine, pentazine, purine, pteridine, diamines and polyethylene polyamine class; (2) contain one or above nitrogen-atoms and contain the fragrant heterocycle or the aliphatic compounds of one or above oxygen, sulphur atom again, example as oxadiazole, oxatriazole, two oxazoles, two oxadiazoles, trioazole, 2-mercaptopyridine, 2-mercaptobenzothiazole, 2-hydroxybenzothiazole, 2-amino benzimidazole, pyrrolidones, two-2-pyridine-glyoxal, pyridine-2-acetate and each seed amino acid and derivative thereof; (3) contain one or above phosphorus atoms and contain the aromatic series and the aliphatic compounds of one or above nitrogen, oxygen, sulphur atom again, 2-diphenylphosphine yl pyridines and 1 for example, two (diphenylphosphine) ethane of 2-etc.And from high molecular polymer, it is then more to be prepared into the compound with described architectural feature part.Here both comprised many natural macromolecular compounds, for example polypeptide class large biological molecule also comprises a large amount of artificial synthetic macromolecules.We can say that all above-mentioned multiple tooth organic molecules can be used as substituted radical and enter macromolecule chain section, make needed macromolecule ligand.For example, partly or entirely quaternized again with polymerization or copolymerization such as vinyl imidazole, vinyl pyrrolidone or vinyl bipyridyls, promptly can be made into such ligand molecular.In addition, monodentate type monomer has also just become multiple tooth type molecule after making high polymer, prepares the part with architectural feature of the present invention thus.Because the compliance of macromolecular chain, so the easier space requirement of satisfying reduction transition state free energy of activation in the catalytic reaction process on the configuration conformation.Such macromolecular compound for example has the homopolymers that contains phosphino-polystyrene and polyvinylpyridine and substitutive derivative thereof, and these are nitrogenous, the phosphorus vinyl monomer each other or with the multiple copolymer of other monoene and polyenoid class monomer.Other vinyl monomer can be nitrogenous, phosphorus, oxygen, sulphur functional group, as acrylonitrile, acrylic acid and ester class, diacrylate diethylene glycol dilaurate etc., can also be pure unsaturated olefin, as divinylbenzene and isoprene etc.After adding diene class monomer or other polyenoid class monomer, what obtain is cross-linked polymer, can not be dissolved, so the multiple tooth heterodesmic mould assembly catalyst that the precursor compound of macromolecule ligand that makes at last and rhodium forms is a heterogeneous catalyst.The thermal stability of multiple tooth heterodesmic mould assembly macromolecule ligand is better, the serviceability temperature of for example crosslinked vinylpyridine copolymer can be up to 240 ℃ about.

According to technical conceive of the present invention, be developed into a series of rhodiums (I) ionic complex catalyst with above (A) or (A ') architectural feature, wherein mainly include the catalyst of following type, show that by the listed contrast experiment's data of example part table 2 of the present invention, table 3 and table 5 and the result of other example they all have catalyzed carbonylation performance preferably: 2-amino-4-picoline type (1)

[Rh (CO) ₂I ₂) ^-Poly 2 vinyl pyridine type (2) Tetramethylethylenediamine type (3)

[Rh (CO) ₂I ₂] ^-Poly N-vinyl imidazole type (4)

[Rh (CO) ₂I ₂] ^-4-vinylpyridine/methyl acrylate copolymer type (5)

[Rh (CO) ₂I ₂] ^-Poly 4 vinyl pyridine type (6) 2-mercaptobenzothiazole type (7)

[Rb (CO) ₂I ₂] ^-The amino benzimidazole type (8) of 2-

The invention provides this class Preparation of catalysts method, be divided into three-procedure and carry out: (1) multiple tooth organic and macromolecular compound preparation: the used multiple tooth organic compound of the present invention uses the commercial reagent usually, or purified processing is standby; And macromolecular compound is further to be processed into required material from commercially available intermediate products a bit, and great majority then are self-control, be by vinyl monomer through free radical initiation, solution or suspension polymerisation or copolymerization and make, polymerization or copolyreaction temperature are 60-90 ℃.For copolymer, for adopting most economical easy preparation approach and can making the sequential structure high conformity of macromolecular chain, the constant feeding that need employing Jiang Dazhi etc. is proposed is than free-radical polymerized method [J.Polym.Sci., Polym.Chem.Ed., 15 (1977) 2961-2970].Molecular weight of high polymer is generally regulated and control by the amount of initiator and the polymerization time that add.In polymerization or combined polymerization raw material vinyl monomer, can add diene or polyenoid class monomer just obtains the cross-linked copolymer polydentate compound, the catalyst of making does not thus dissolve in reaction system, and is appropriate swelling.If usefulness is diacrylate diethylene glycol dilaurate class, the swelling behavior of copolymer of making and even last catalyst is good, dissociates but have partial cross-linked key in the certain reaction medium; And if the employing divinylbenzene is made crosslinking agent, catalyst mechanical strength of then finally making and stability are better, though swelling behavior is poor slightly, but resin particle inside can be by generation macropores such as interpolation pore-foaming agents, to reduce diffusion-restricted and steric restriction, alleviate and to eliminate may influence catalytic activity; (2) quaternary saltization: the nitrogen, the phosphorus group that are about in the multiple tooth organic and macromolecular compound partly or entirely become the quaternary salt ion.For this reason, polydentate compound is joined among quaternary salt reagent iodomethane etc., perhaps again with benzene, acetone or the dilution of alcohols equal solvent, the stirring and refluxing reaction is 0.5-24 hour in the round-bottomed flask that agitator and condenser are housed, pressure reducing and steaming solvent or through suction filtration, washing, drying under reduced pressure promptly gets part or all of quaternary salt part; Sometimes also can be with the vinyl monomer of selected nitrogenous, phosphorus functional group, first quaternary saltization is made required degree of cross linking or the linear macromolecule ligand again; When preparation organic molecule and vinyl monomer quaternary salt, also thick part goods can be dissolved in the absolute ethyl alcohol of boiling, place ice-water bath to be recrystallized again, crystalline solid is standby with absolute ether washing, drying under reduced pressure; The quaternary salt part also can be in the carbonylation medium original position form, be about to polydentate compound and directly join in the carbonylation reaction system that contains the iodomethane co-catalyst, place or course of reaction in, described polydentate compound is quaternary saltization to a certain extent just; The quaternary salt degree is controlled by phase mutual edge distance and structural factor in the selected multiple tooth organic and macromolecular compound molecular skeleton between nitrogen, the phosphorus functional group, need change quaternary salt reagent dosage, strict control reaction temperature and reaction time sometimes to obtain desirable structure; (3) multiple tooth heterodesmic mould assembly rhodium (I) ionic complex is synthetic: the multiple tooth organic or macromolecule ligand and four carbonyl dihalo-s, the two rhodium [Rh that make more than inciting somebody to action ₂(CO) ₄X ₂] (X=I; Br; Cl), the content that accounts for 0.5-25wt% by rhodium in catalyst carries out proportioning; join in benzene or alcohols equal solvent or its mixed solvent; under room temperature and argon shield stirring reaction 0.5-4 hour, dry naturally or remove after filtration and desolvate drying under reduced pressure; product is generally faint yellow particle or crystalline powder to pale brown look even Dark grey, but places long preservation in the drier.Infrared spectrum detects at 2059-2068cm ^-1And 1981-1989cm ^-1Respectively there is a strong carbonylic stretching vibration absorption band at two places, and showing has [Rh (CO) ₂X ₂] ^-(X=I, Br, existence Cl).Nitrogenous, the phosphorus of institute should be controlled between the 2-100 the ratio of rhodium atom in the catalyst ligand, be preferably in the 5-30 scope, and the nitrogen, the phosphorus group (L that occur with the quaternary salt ionic species in the part ⁺) with the ratio that has probability of the nitrogen that occurs with free base form, phosphorus, oxygen, sulphur part unit (L °), different with reaction system and suitably controlled with the concrete structure of ligand molecular, usually should be between 0.1-3, preferably in the 0.2-1 scope.Multiple tooth heterodesmic mould assembly rhodium (I) ionic complex catalyst also can original position form in carbonylation reaction system, be about to the precursor compound of multidentate ligand and rhodium, as four carbonyl dihalo-s, two rhodiums or rhodium chloride hydrate, by the concentration of rhodium in reaction system is that the proportioning of 0.1-50mmol/L directly is added in the reaction medium, closed reactor, charge into CO, pressure is 0.3-6.0MPa, in intensification or course of reaction, just automatically form described rhodium ion composition catalyst, logically can detect the anionic appearance of dicarbapentaborane diiodo-rhodium (I) in-situ ft-ir.

Adopt multiple tooth heterodesmic mould assembly rhodium catalyst of the present invention, by methyl alcohol through carbonylation system acetate and methyl acetate, or by methyl acetate and/or dimethyl ether through carbonylation system acetic anhydride, not only have high catalytic activity and high selectivity, its reaction condition-particularly reaction temperature can be accomplished more gentle; On the other hand because the design feature of catalyst itself and in reaction system and the chemical compatibility between each part can further improve, thereby improved stability, the particularly thermal stability of catalyst in carbonylation reaction system.

The using method of catalyst of the present invention, with industrial current technology basically identical, promptly earlier with multiple tooth heterodesmic mould assembly rhodium (I) ionic complex catalyst (or precursor compound of multidentate ligand and rhodium), material benzenemethanol (using when system acetate and methyl acetate) or acetate methyl alcohol (using during the system acetic anhydride), also has co-catalyst, other auxiliary agent and additive join in the reactor in the room temperature metering according to a certain ratio, airtight, with twice of CO purge of gas, charge into the carbonylation pressure limit of CO reacting gas again to appointment, and be warmed up to the reaction temperatures for carbonylation will interval of appointment, clock reaction, observed and recorded CO infiltration rate, and get the gas sample respectively and the liquid sample is done gas chromatographic analysis.Perhaps in room temperature inflation a little earlier, fill reaction gas again after waiting to be warmed up to the assigned temperature interval, and under constant pressure air feed, clock reaction, and sample analysis.After reaction finishes,, or cool off with ice-water bath again, open the gas of emitting before the still through gas chromatographic analysis earlier with being water-cooled to room temperature; Measure reactant liquor after driving still, with gas-chromatography or again with titration measuring reactant liquor composition.

The co-catalyst that the present invention adds in carbonylation reaction system is halide, particularly iodomethane; Other auxiliary agent and the additive that may add have slaine, particularly metal lithium salts-lithium iodide and lithium acetate, and solvent acetic acid, methyl acetate or acetic anhydride.The iodomethane consumption should remain between the 0.5-8mol/L, normally 1-5mol/L as with the densimeter in reactant liquor; Iodide account for more than 60% of halogen compounds mole total amount in the reaction medium.When being added with the metal lithium salts in reaction system, latter's content in reactant liquor should be preferably between the 5-15wt% in the 1-20wt% scope; As so that wherein lithium metal (Li) is to the ratio (Li/Rh) of rhodium atom, this value generally is at 10-500, preferably between 60-250.In reaction system of the present invention, what add as solvent is acetate, methyl acetate or acetic anhydride, and its effect is that not only they are fine solvents, can make that the chemical compatibility between each key component can be better in the reaction system; Being also on the other hand that they have carbonylation induces and facilitation, is favourable to improving rate of catalysis reaction.Especially in carbonylation system acetic anhydride reaction system, their slaine that is beneficial to as promoter that has in a large number occurs with the acetate form, thus easier the carrying out of formation that can cause catalytic reaction end product acetic anhydride.For methanol carbonylation, the primary solvent of adding is an acetate, and the addition by volume can account for the 5-90% of reaction medium, preferably is controlled in the 20-55% scope; When producing acetic anhydride, adding more is methyl acetate, and this moment, the latter itself also was a raw material, and the total concentration in reactant liquor is controlled in the 3-8mol/L scope, and methyl acetate/acetate mol ratio should be controlled in the 1-10 scope, preferably between the 3-6.

The important difference that carbonylation method is produced acetic anhydride and acetate is: the system acetic anhydride reaction medium, comprise that caltalyst ties up in, should be anhydrous basically; In addition, some metallic compound promoter effect in the catalyst system of acetate carbonyl system acetic anhydride, more more obvious and important than role in the carbonylation of methanol system acetic acidreaction process.

The carbonylation experiment of adopting various catalyst of the present invention to carry out has proved that they all have good catalytic performance.Reaction condition is gentle relatively, can use in 120-210 ℃ of scope, and is preferable to be controlled at the 140-180 ℃ of effect in the scope.The CO dividing potential drop if can remain on more than the 0.3MPa in reaction system, and carbonylation can carry out.Raw material and reaction gas gross pressure are 2.6-8MPa in the reactor, generally are controlled in the 3-6MPa scope, and wherein the CO dividing potential drop preferably remains on more than the 1.5MPa.

The present invention has overcome a series of shortcomings of prior art to having the improvement that carbonylating catalyst and technology thereof are carried out now, and effect is significant in the following areas:

Catalyst that the present invention formulated and system thereof both can be applicable to carbonylation of methanol and had produced acetate, also can be applicable to acetate carbonyl system acetic anhydride.When being used for carbonylation of methanol, need not to add water and hydrogen iodide in the reaction system and come rugged catalyst and active specy thereof to keep catalytic activity, so water content greatly reduces in the product that initial separation is come out, thereby can save the energy consumption that is further purified products of separated.Also this characteristics just change catalyst system of the present invention a little, and promptly can be used for methyl acetate and dimethyl ether is that raw material is produced acetic anhydride, because the reaction medium of carbonylation system acetic anhydride should be an anhydrous system.And when being used for methyl acetate and dimethyl ether carbonylation production acetic anhydride, although it is anhydrous that reaction system requires, also do not hinder but contain the minor amount of water that comprises the crystallization water in the material that adds, that is the material that contains the crystallization water or minor amount of water can directly use with before need not work except that water treatment.

From the appended example of the present invention as can be seen, adopt catalyst of the present invention under comparatively gentle reaction condition, particularly in lower pressure and temperature scope, to realize the carbonylation method production of acetate and acetic anhydride, the reaction gross pressure is generally at 3-6MPa, and temperature is 140-180 ℃.Relatively low reaction temperature can prolong service life of catalyst, to reactor design, material select, reduce operation energy consumption and production safety all favourable.In view of reaction temperature can drop to 180 ℃ and following, the abstraction reaction product also can adopt flash process from reaction system, and uses common evaporation technique instead.Under latter instance, adopt CO gas by the base of evaporator bubbling, prevent bumping and promote evaporation to carry out, so more help protection to catalyst activity species in the mother liquor that recycles.

Catalyst of the present invention is used for carbonylation very high selectivity.Gas-liquid mixed and stir good and can keep reaction temperature to divide and be pressed in 1.5MPa and total still is pressed under the above situation of 2.6MPa in reactor at 150-180 ℃, CO, the carbonylation of methanol product is except that acetate and methyl acetate, even additionally do not add water, the dimethyl ether growing amount also can be controlled to seldom, even can not detect.And dimethyl ether can participate in reaction voluntarily again in reaction system, all is converted at last to be carbonylation product, so the carbonylation selectivity can reach more than 99%.And when methyl acetate and dimethyl ether carbonylation, in the reaction system as anhydrous interference, the carbonylation selectivity is 100%.

Because the present invention adopts the multiple tooth organic and macromolecule ligand contain the nitrogen that is in the different chemical state, phosphorus, oxygen, sulphur, makes it to combine with rhodium with heterodesmics such as ion pair and the ligand complex form of closing.The carbonylation experimental result shows, this with multiple tooth quaternary salt type part unit be integrated in one with free base part unit, again with the rhodium catalyst that forms of bonding mutually, in reaction system and the chemical compatibility between reactant and the product, stability, especially heat endurance and catalytic activity all be significantly improved, this is most important to comprehensive serviceability of improving catalyst, the rhodium loss that reduces in catalytic reaction and the product separation process.The ionic compound that single quaternary salt type part and rhodium form in pyroreaction, particularly be easy to decompose in the high temperature flash process, causes the rhodium inactivation to precipitate.And the simple complex that contains the nitrogen, phosphorus part and the rhodium formation that are in free base state fully, its catalytic activity is not as the former.In fact catalyst of the present invention is not only heat endurance, and aspect catalytic activity, and also the full quaternary salt type part that exists than no free base part unit is good with the catalyst of dicarbapentaborane diiodo-rhodium (I) anion formation.Compare with the composition catalyst of complete free base part bonding rhodium carbonyl, catalyst of the present invention not only is greatly improved aspect catalytic activity, even aspect thermal stability, the latter in fact also can not be by comparison.This is because latter's chemical compatibility can be poor, coking promptly occurs and sink to the bottom phenomenon in high temperature carbonylation reaction system more than 140 ℃, and catalytic activity reduces on the contrary, so only should be 140 ℃ and the use of following temperature.And catalyst serviceability temperature of the present invention can reach 210 ℃, and normally used reaction temperature is 140-180 ℃.Reaction temperature can reach and has the enough catalytic rate and the space-time yield of good industrial application value more than 140 ℃ the time.Outwardly, the crucial part of the present invention is that with both combinations its actual effect but is to have brought into play both advantages, eliminated deficiency separately, and comprehensive effect is fairly obvious, has demonstrated fully the part sum less than whole this complexity theory rule.

The catalytic activity of catalyst of the present invention is higher than existing similar catalyst, and no matter its stability and space-time yield with regard to carbonylation system acetate is still made acetic anhydride, all are far longer than present commercial production levels.In example 4-8 and 13-16, the present invention adopts dissimilar compounds as catalyst, respectively the catalytic reaction activity of carbonylation of methanol and acetate carbonylization has been carried out experiment relatively.The data that are listed in table 2 and the table 3 are pointed out, example 6 and 15 catalyst system therefors 1 be the 2-amino-4-picoline mono-quaternaries of multiple tooth heterodesmic mould assembly suitable-dicarbapentaborane diiodo-rhodium compound, the 4-picoline quaternary ammonium salt of comparison example 4 and 13 used monodentate types is suitable-dicarbapentaborane diiodo-rhodium compound 1s, and the former exceeds more than 1/3rd than the latter catalyzed carbonylation activity.And example 5 and 14 used two ligand complex type catalyst 1a, promptly 2-amino-4-picoline suitable-dicarbapentaborane rhodium cationic compound, its activity then only reaches the 74-77% of 1s.The used catalyst 3 tetramethyl second two ammonium mono-quaternaries of example 7 are suitable-and dicarbapentaborane diiodo-rhodium and example 8 and 16 used multiple tooth heterodesmic mould assembly high polymer parts are suitable-dicarbapentaborane two iodine catalysts 2, all shown the high catalytic activity of this compounds of multiple tooth heterodesmic mould assembly rhodium (I) ionic complex to carbonylation.

The present invention can make multiple tooth heterodesmic mould assembly rhodium (I) ionic complex catalyst with many organic and macromolecular compounds that contain multiple tooth nitrogen, phosphorus, oxygen, sulphur functional group.Some did not have the integration thing of the rhodium of catalytic activity to adopt method of the present invention originally, can also become to have highly active catalyst.Can also see from example 23, adopt a cover Preparation of Catalyst and a treatment technology proposed by the invention, the multidentate ligand change that is easy to transition metal active centres formation chelate structure can be become the multiple tooth heterodesmic mould assembly part with architectural feature of the present invention, thereby make the multiple tooth heterodesmic mould assembly rhodium catalyst that forms thus have high catalytic reaction activity.In carbonylation reaction system, not only do not have catalytic activity, and in fact also can make rhodium in the catalyst that certain catalytic activity was arranged originally because of forming the chelate poisoning and deactivation of non-activity again without the chelate of so transforming.

Catalyst of the present invention also has an advantage, and that Here it is is nitrogenous, the multiple tooth organic and macromolecule ligand of phosphorus, oxygen, sulphur, both can make low-molecular-weight organic matter or oligomer, and the catalyst of formation is solvable fully in reaction system, is applicable to the homogeneous phase solution reaction; Also can make the copolymer ligand of high-crosslinking-degree, the catalyst of formation is no longer dissolving in reaction system, and is appropriate swelling, and changing homogeneous reaction is that heterogeneousization carried out.Under latter instance, the leakage of metal active center rhodium can be by selecting appropriate solvent and regulate high polymer/metal ratio to reduce to minimum in the catalyst.Homogeneous phase of making like this and heterogeneous two class catalyst, because Heat stability is good, and contain the multiple tooth functional group that chemical compatibility can be splendid in its part, this makes them not be prone to catalyst and the attached wall of metal thereof in carbonylation equipment, sink to the bottom with coking and be difficult to remove.

Example 1

10.8g 2-amino-4-picoline (2A4MPy) is dissolved in the 60ml acetone, adds the 18.2g iodomethane again, stirring and refluxing reaction 10 hours, placement is spent the night.Filter, with the acetone washing, drying under reduced pressure gets the pale brown look mono-quaternaries of 24.1g part ([2A4MPy-CH ₃] ⁺I ^-).Gained part 0.25g is dissolved in the 5ml methyl alcohol, adds 0.1940g four carbonyl dichloros two rhodiums under room temperature and argon shield, stirred 15 minutes, place nature and dry drying under reduced pressure.Get 5mg product and pressing potassium bromide troche, infrared spectrum is at 1987cm ^-1And 2065cm ^-1The carbonylic stretching vibration absorption band at place shows has following reaction to produce:

This product is being rich in iodine anion (I ^-) solution in, the chlorine on the rhodium ion is easy to by iodization, becomes to be [2A4MPy-CH ₃] ⁺[Rh (CO) ₂I ₂] ^-(catalyst 1 type).

In 250ml zirconium material reactor, put into 95.0g methyl alcohol and 68.4g iodomethane, above catalyst 0.1418g and part 2.0g thereof in room temperature.Rhodium concentration is 2.56mmol/L in reaction system.Sealed reactor.Remove air in the still with CO, be warming up to 140 ℃, keep pressure 2.6-4.2MPa, stir 500 rev/mins, reacted 2.5 hours.Methyl acetate and acetate growing amount are respectively 0.59mol and 0.34mol, and rate of catalysis reaction (TON) is 968mol AcOH/mol Rh-h.

Another time experiment is in being full of the 250ml zirconium still of CO, is placed with quaternary ammonium salt part 2.0g, four carbonyl dichloros, two rhodium 0.062g, water 23.1g, methyl alcohol 37.0g, iodomethane 52.0g, methyl acetate 13.7g and the acetate 63.7g of above preparation.Rhodium concentration 1.90mmol/L in the reaction system.Be warming up to 170 ℃, keeping the still pressure with CO is 3.7MPa, stirs 500 rev/mins, reacts 1 hour.Methanol conversion 98.8%, methyl acetate and acetate increment are respectively 0.07mol and 1.0mol, catalytic rate 3358mol AcOH/mol Rh-h.

Testing used CO purity is 92-93%, and other contains CO ₂0.5-0.9%, H ₂3-4%, O ₂0.5-0.6%, N ₂1-3%, all the other are the compound of steam, denier sulphur.The used CO source of the gas of following example all is like this.

Example 2

In three mouthfuls of round-bottomed flasks of 150ml, 2-vinylpyridine (2VPy)-its polymers of divinylbenzene 10g of 40-80 order 15% degree of cross linking is swollen in the 50ml ethanol, the salinization intensity different basis weights adds iodomethane quaternary salt reagent quarterly, 50 ℃ of back flow reaction of temperature control 6 hours, again in stirring at room 6 hours, filter, with the ethanol washing, drying under reduced pressure gets the 2-vinylpyridine-divinylbenzene copolymer (PVPy215) of different quaternized degree 15% degrees of cross linking.Pyridine group quaternization degree the results are shown in Table 1 in the determination of elemental analysis copolymer.Under room temperature and argon shield, with four carbonyl dichloros, two rhodiums stirring reaction 4 hours in methyl alcohol, suction filtration, vacuum drying makes the product that the rhodium-containing amount is 2wt% (PVPy215/Rh) respectively with the copolymer ligand of different quaternization degrees, and infrared spectrum is at 1981cm ^-1And 2068cm ^-1There is the carbonyl absorption band at the place, and showing has [Rh (CO) ₂X ₂] ^-(X=Cl, existence I).In reaction system, its typical construction unit is catalyst 2 types.

Methanol carbonylation carries out in 250ml zirconium still.Put into the catalyst 3.0g of still methyl alcohol 95.0g, iodomethane 54.7g and above-mentioned preparation, sealed reactor with air in the CO displacement still, is warming up to 140 ℃, and constant voltage is at 3.1MPa, and mixing speed is 450 rev/mins, reacts 1 hour, and chromatography is carried out in sampling.Table 1 is listed the catalytic activity experimental result of the catalyst 2 (PVPy215/Rh) of different quaternization degrees.

Table 1. catalyst 2 quaternization degrees are to the influence of carbonylation of methanol catalytic activity

Quaternized degree %	Rh concentration mmol/L	Space-time yield mol AcOH/L-h	TON mol AcOH/mol Rh-h	Methanol conversion %
					0	4.05	2.53	624.4	43.4
20	4.07	4.10	1006.2	55.6
					40	4.12	3.45	838.5	54.8
60	4.00	3.10	773.9	48.0
					80	4.10	2.71	707.0	45.0

Example 3

Catalyst and preparation thereof are quaternized with example 2,42% pyridine rings.In 250ml zirconium reactor, be placed with the 162ml reactant liquor, wherein methyl alcohol 92.8g, iodomethane 57.4g, methyl acetate 12.4g, water 6.2g and catalyst 2.08g.Rhodium concentration is 2.50mmol/L in the reaction system.Fill CO and remove air in the still, be warming up to 150 ℃, keep still and press 4.5MPa, stir 500 rev/mins, reacted 1 hour.Methyl acetate and acetate increment are respectively 0.46mol and 0.26mol, catalytic rate 1781mol AcOH/mol Rh-h.

Another time experiment is placed with the 135ml reactant liquor in being full of the 250ml zirconium still of CO, wherein contain catalyst 2.08g, lithium iodide 6g, methyl alcohol 25.5g, iodomethane 36.0g, methyl acetate 10.3g, acetate 68.3g and water 10.7g.Rhodium concentration is 2.99mmol/L in the reaction system.Be warmed up to 140 ℃, with CO constant voltage 4.0MPa, 700 rev/mins of mixing speeds were reacted 20 minutes.Methyl acetate and acetate increment are respectively 0.27mol and 0.14mol in the reactant liquor, and catalytic rate is 3073mol AcOH/mol Rh-h.

Example 4-8

Example 4-8 has done experiment relatively to the catalytic activity that relevant catalyst is used for carbonylation of methanol.Experiment is carried out in 25ml zirconium material reactor.Material methyl alcohol 7.92g, iodomethane 5.70g and a certain amount of catalyst that each experiment is put into.Airtightly remove air in the still, charge into CO to 4.0MPa, be warming up to 135 ℃, reacted 1 hour, be cooled to the pressure drop of room temperature record, continue again with cryosel water-bath cooling.Gas-liquid is formed in the gas chromatographic analysis still, and calculates catalytic reaction velocity constant (k), and relevant data the results are shown in table 2.

Table 2. carbonylation of methanol catalyst activity relatively

Instance number	Catalyst	Rhodium concentration [Rh] mmol Rh/L	Carbonylation product increment mmol	Velocity constant k * L/mol/min	Velocity constant compares k/ks
						4	1s	2.92	10.8	1.54	1.00
5	1a	2.48	6.8	1.14	0.74
						6	1	3.00	15.3	2.12	1.38
7	3	2.57	12.7	2.05	1.33
						8	2	2.78	14.9	2.23	1.45

* the k value is calculated according to carbonylation kinetics equation: reaction speed=k[Rh] [McI] catalyst 1s be 4-picoline methyl quaternary ammonium suitable-dicarbapentaborane diiodo-rhodium (I) complex:

1s catalyst 3 be the tetramethylethylenediamine mono-quaternaries suitable-dicarbapentaborane diiodo-rhodium (I) complex.The preparation of catalyst 1s and 3 these two kinds of compounds is respectively by 4-picoline (4MPy) and N, N, and N ', N '-tetramethylethylenediamine sets out, and is quaternized and final synthetic with example 1.

Example 5 catalyst 1a be 2-amino-4-picoline suitable-dicarbapentaborane rhodium (I) cationic complexes:

Its preparation method is: with mole ratio is that 2: 1 2-amino-4-picoline and four carbonyl dichloros, two rhodiums are dissolved in methyl alcohol respectively and place cryosel to bathe, and under stirring and CO protects, the latter solution is dropwise joined in the former solution.After all adding, continue to stir 10 minutes.Adding the appropriate amount tetraphenylboron sodium, with sedimentation and filtration, is that 4: 1 methanol-water solution fully washs with volume ratio, and drying under reduced pressure is standby.Infrared spectrum is at 2063cm ^-1And 2006gm ^-1The carbonylic stretching vibration absorption band that two places are strong, and X-photoelectron spectroscopy (XPS) points out not exist in the product chlorine, the existence of confirmation said structure.

Example 9

With the 10g molecular weight is that 1.2 ten thousand poly N-vinyl imidazoles (PNVI) is dissolved in 60ml methyl alcohol, adds the 15g iodomethane again, stirring and refluxing reaction 20 hours, and the cooling suction filtration is washed with methyl alcohol, dry pale brown chromoresin part ([PNVI-CH ₃] ⁺I ^-), 44.6% nitrogen is quaternized on the imidazole ring.The 5.0g part is placed 20ml methyl alcohol, add 0.3270g four carbonyl dichloros two rhodiums, under room temperature and argon shield, stirred 15 minutes, place nature and dry, drying under reduced pressure is standby.In carbonylation reaction system, its typical structure unit is catalyst 4 types.

In 250ml zirconium still, catalyst 1.57g, lithium iodide 7.5g, methyl alcohol 47.5g, iodomethane 75.4g, methyl acetate 42.7g, acetate 6.3g and water 5.1g that to add above rhodium-containing amount be 3.25wt%, rhodium concentration is 3.31mmol/L in the reaction system.Logical CO is warming up to 150 ℃, keeps still and presses 4.0MPa, stirs 500 rev/mins, reacted 1 hour, methanol conversion 87.1%, methyl acetate and acetate increment are respectively 0.30mol and 0.69mol, catalytic rate 1997mol AcOH/mol Rhh, space-time yield 6.6mol AcOH/Lh.

Another time experiment is that the poly N-ethylene imidazoles-divinylbenzene copolymer 10g with 20-40 order 34% degree of cross linking joins in the 114g iodomethane, stirring and refluxing reaction 2 hours, the unnecessary iodomethane of filtered and recycled, drying under reduced pressure, yellow resin ligand 1 8.5g.48% nitrogen is by quaternized on the elementary analysis imidazole ring.In 250ml zirconium still, put into cross-linked copolymer part 2.5g, RhCl ₃3H ₂O 252.0mg and lithium iodide 8.27g, after educating through one section carbonylation environment wine, the typical structure unit of catalyst also is catalyst 4 types in the reaction system.Drop to 50 ℃ of blowings in temperature, product of distillation, the mother liquor pump is same in reactor, and prepare burden again: contain methyl alcohol 82.2g, iodomethane 86.0g, methyl acetate 25.1g, acetate 2.5g and water 11.3g in the reaction system, rhodium concentration is 5.26mmol/L in the reaction system.Connect the CO source of the gas, be warming up to 160 ℃, keep still and press 4.0MPa, reacted methanol conversion 52.3%, carbonylation product increment 0.90mol, space-time yield 14.9mol AcOH/Lh, catalytic rate 2823mol AcOH/mol Rhh 20 minutes.

Example 10

With 30ml 4-vinylpyridine (4VPy) and 11ml methyl acrylate (MA) copolymerization.NMR spectrum and elementary analysis show that the ratio (4VPy/MA) of two kinds of comonomer units is close to 1 in the copolymer.Gained dry resin 10g is dissolved in 60ml benzene and the 20ml methyl alcohol mixed liquor, adds the 10.0g iodomethane, stirring and refluxing reaction 16 hours is again in stirring at room 6 hours.Filter, successively wash with benzene and methyl alcohol, drying, measuring has 90% pyridine ring quaternized.The light yellow resin part of gained 5g is placed 20ml benzene and 10ml methyl alcohol mixed solvent, add the methanol solution of 0.1260g four carbonyl dichloros two rhodiums, stirring reaction is 1 hour under room temperature and argon shield; filter; drying under reduced pressure, getting the rhodium-containing amount is the catalyst of 1.3wt%, infrared spectrum is at 1989cm ^-1And 2065cm ^-1There is the strong absorption band of carbonylic stretching vibration at the place.In reaction system, its typical construction unit is catalyst 5 types.

In 250ml zirconium still, put into 2.05g catalyst, 79.2g methyl alcohol, 45.6g iodomethane and 10.0g water, rhodium concentration 1.99mmol/L in the reaction system.Remove air in the still, add CO to 2.5MPa, be warming up to 140 ℃, keep total still and be pressed in 3.0-4.3MPa, stir 450 rev/mins, reacted 1 hour.Methyl acetate and acetate growing amount are respectively 0.24mol and 0.07mol, catalytic rate 1197mol AcOH/mol Rh-h.

Example 11

4-vinylpyridine-divinylbenzene copolymer (PVPy405) 10g with 40-80 order 5% degree of cross linking swells in the 50ml ethanol, adds the 4.6g iodomethane, stirring and refluxing reaction 16 hours was cooled to stirring at room 4 hours, filtered, with the ethanol washing, drying under reduced pressure, quaternary salt degree are 35%.Adopt as example 2 methods, it is 2wt% catalyst (PVPy405/Rh) that this part is made the rhodium-containing amount.In reaction system, its typical structure unit is catalyst 6 types.

In 250ml zirconium still, put into catalyst 2.08g, methyl alcohol 79.2g and the iodomethane 45.6g of above preparation.Rhodium concentration is 3.37mmol/L in the reaction system.Fill CO and remove air in the still, be warmed up to 140 ℃, keep still and be pressed in 2.5-4.0MPa, stir 500 rev/mins, reacted 1 hour.Methyl acetate and acetate growing amount are respectively 0.47mol and 0.14mol in the chromatography liquid phase, catalytic rate 1508mol AcOH/mol Rh-h.

Example 12

Get 2-mercaptobenzothiazole 10g and place 80ml benzene, add the 10.0g iodomethane, stirring and refluxing reaction 6 hours is cooled to room temperature, stirs 4 hours again, filters, and washes with benzene, and drying under reduced pressure again 60 ℃ of vacuum drying 3 hours, gets dark gray powder.Adopt as example 1 method, this part 0.25g is dissolved in the 5ml methyl alcohol, it is standby that catalyst is made in the reaction of adding 0.1571g four carbonyl dichloros two rhodiums.In reaction system, its typical construction unit is catalyst 7 types.

In 250ml zirconium still, put into above catalyst 0.123g, water 1.0g, methyl alcohol 57.4g and iodomethane 56.8g, methyl acetate 19.2g, acetic acid 22.8g and lithium acetate 2.3g, rhodium concentration 1.73mmol/L in the reaction system.Fill CO and remove air in the still, be warming up to 160 ℃, keep still and press 3.8MPa, stir 450 rev/mins, reacted 1 hour.Methyl acetate and acetate increment are respectively 0.49mol and 0.15mol, catalytic rate 2580mol AcOH/mol Rh-h.

Example 13-16

The catalytic activity that example 13-16 is used for acetate carbonyl system acetic anhydride with aforementioned relevant catalyst has been carried out the experiment contrast, relevant data and the results are shown in table 3.

Table 3. acetate carbonyl system acetic anhydride catalyst activity relatively

Instance number	Catalyst	Rhodium concentration [Rh] mmol Rh/L	Carbonylation product increment mmol	Velocity constant k a L/mol/min	Velocity constant compares k/ks
						13	1s	2.81	11.2	2.07	1.00
14	1a	3.18	9.8	1.60	0.77
						15	1	2.98	16.2	2.82	1.36
16	2	2.73	15.7	2.99	1.44

The a.k value calculating method is with table 2 footnote.Experiment is carried out in 25ml zirconium still.Each experiment drops into methyl acetate 3.73g, iodomethane 4.56g, acetate 5.24g and lithium acetate 0.2-0.3g, and a certain amount of catalyst.Closed reactor is removed air, fills CO to 4.1MPa in room temperature, is warming up to 140 ℃, reacts 1 hour, is cooled to the pressure drop of room temperature record.Gas-liquid is through gas-chromatography and titration measuring in the still, calculates rate constant (k) and makes comparisons, and is as shown in table 3.

Example 17

Catalyst is the 4-vinylpyridine-divinylbenzene copolymer of 15% degree of cross linking of different quaternized degree and rhodium (I) ionic complex (PVPy415/Rh) that four carbonyl dichloros, two rhodiums form, and the quaternized and method for preparing catalyst of copolymer is with example 2.Its typical structure unit is catalyst 6 types (examples 11) in reaction system.Be reflected in the 250ml zirconium still and carry out.Put into still methyl acetate 56.3g, iodine alkane 78.0g, acetic acid 27.6g, aceticanhydride 17.3g and lithium acetate 4.2g, and a certain amount of above-mentioned catalyst.Fill CO and remove air in the still, be warming up to 160 ℃, constant voltage 4.0MPa, 350 rev/mins of mixing speeds were reacted sample analysis 1 hour.Table 4 is the catalytic activity experimental result of the catalyst 6 of different quaternized degree.

The influence of table 4. catalyst 6 quaternized degree Dichlorodiphenyl Acetate methyl esters carbonylation catalytic activitys

Quaternized degree %	Rh concentration mmol/L	Space-time yield mol Ac 2O/L-h	TON mol Ac 2O/mol Rh-h	AcOMe conversion ratio %
					0	1.88	0.97	518.0	17.6
10	1.86	1.71	918.7	31.1
					20	1.69	1.79	1060.0	32.6
30	1.63	1.79	1098.1	32.6
					50	1.70	1.65	970.0	30.0
70	1.72	1.42	823.2	25.8
					100	1.72	1.38	800.0	25.1

Example 18

Catalyst is with example 1.In 250ml zirconium still, put into catalyst 0.1415g and quaternary ammonium salt part ([2A4MPY-CH thereof ₃] ⁺I ^-) 2.0g, methyl acetate 48.2g, iodomethane 58.4g, acetate 30.6g, acetic anhydride 61.3g and lithium acetate 3.9g.Rhodium concentration is 1.95mmol/L in the reaction system.Remove air in the still with CO, be warming up to 170 ℃, keep still and press 4.0MPa, stir 500 rev/mins, reacted 1 hour.Acetic anhydride increment 0.44mol, catalytic rate 1348mol AcOAc/mol Rh-h.

Example 19

Catalyst and method for making thereof are with example 3, but the rhodium-containing amount is 1.48wt%.In 250ml zirconium still, put into 2.2g catalyst, 50.8g methyl acetate, 52.0g iodomethane, 28.5g acetate, 48.1g acetic anhydride and 4g lithium acetate in room temperature.Rhodium concentration is 2.12mmol/L in the reaction system.Fill CO and remove air in the still, be warming up to 180 ℃, keep still and press 4.0MPa, 500 rev/mins of mixing speeds were reacted 1 hour.Acetic anhydride increment 0.59mol, space-time yield 4.0mol/L-h, catalytic rate 1868mol AcOAc/mol Rh-h.

Example 20

Catalyst ligand is the poly N-ethylene imidazoles-divinylbenzene copolymer of used 20-40 order 34% degree of cross linking of the 2nd experiment of example 9, and 48% nitrogen is by quaternized on the imidazole ring.In 250ml zirconium still, put into ligand 1 .91g, RhCl ₃3H ₂O 252.0mg and AcOLi2H ₂O6.30g, behind one section carbonylation, the typical structure unit of catalyst is a catalyst 4 shown in the example 9 in the reaction system.Blowing when temperature drops to 60 ℃, product of distillation, mother liquor is pumped back in the still batching again: contain iodomethane 75.4g, methyl acetate 94.5g, acetate 29.7g and acetic anhydride 28.2g in the reaction system, rhodium concentration is 5.06mmol/L in the reaction system.Logical CO is warming up to 180 ℃, keeps still and presses 4.0MPa, stirs 500 rev/mins, reacts 15 minutes.Methyl acetate conversion ratio 41.5%, acetic anhydride increment 0.53mol, catalytic rate 2218mol AcOAc/mol Rhh, acetic anhydride space-time yield 11.2mol/Lh.

Example 21

Catalyst is fully with example 10.In 250ml zirconium still, be placed with the 182.6ml reactant liquor, wherein contain methyl acetate 60.6g, iodomethane 74.1g, acetate 89.3g, contain the lithium acetate (AcOLi2H of two crystallizations water ₂O) 7.44g and catalyst 2.90g.Rhodium concentration is 2.0mmol/L in the reaction system.Logical CO removes air in the still, heats up and maintains 138-143 ℃, keeps total still and presses 4.0-4.2MPa, stirs 500 rev/mins, reacts 1 hour.Methyl acetate conversion ratio 33.6%, moisture content complete obiteration in the reaction system, acetate and acetic anhydride increment are respectively 0.29mol and 0.13mol, catalytic rate 753mol AcOAc/mol Rh-h.

Example 22

Catalyst and method for making thereof are with example 11, but rhodium content is 1.38wt%.In 25ml zirconium still, put into catalyst 0.2167g, methyl acetate 3.73g, acetate 5.24g, iodomethane 4.56g and AcOLi2H ₂O 0.46g.Behind air in the CO removing still, to suck dimethyl ether, the dimethyl ether amount that sucks of weighing is 3.08g with the liquid nitrogen frozen reactor.Rhodium concentration is 1.86mmol/L in the reaction system.Fill CO to 4.0MPa, be warming up to 140 ℃, gross pressure rises to 5.0MPa, reacts 1 hour, and reactor is cooled to room temperature.Gas is collected through liquid nitrogen cold trap in the still, places dry ice-propanone to bathe volatilization again.Gas and kettle base solution body that analyze to collect are determined moisture content complete obiteration, and acetate increment and acetic anhydride growing amount are respectively 17 and 18mmol, catalytic rate 901mol AcOAc/mol Rh-h.

Example 23

Get 2-amino benzimidazole 10g and place 80ml benzene, add the 12.8g iodomethane, stirring and refluxing reaction 8-10 hour is cooled to room temperature, stirs 1 hour again, filters, and with benzene washing, drying under reduced pressure, again 60 ℃ of vacuum drying 3 hours, gets brown powder.Adopt then as example 1 same quadrat method, this part 0.25g and four carbonyl dichloros, two rhodium 0.1767g are reacted in methyl alcohol to make catalyst standby.In reaction system, its typical construction unit is catalyst 8 types.

In 250ml zirconium still, put into above catalyst 0.112g, iodomethane 74.9g, methyl acetate 56.3g, acetic acid 29.0g, aceticanhydride 29.3g and lithium acetate 2.3g, liquid-phase reaction system meter 148ml, wherein rhodium concentration is 1.61mmol/L.Fill CO and remove air in the still, be warming up to 160 ℃, keep still and be pressed in 4.0MPa, stir 400 rev/mins, reacted 1 hour.Aceticanhydride increment 0.30mol, catalytic rate 1259mol AcOH/mol Rh-h.

The amino benzimidazole of 2-is easy to form chelating type rhodium (I) compound (8a) structure with the transition metal rhodium compound:

The 8a contrast experiment: catalyst is selected the ionic complex catalyst 8 and chelate 8a with architectural feature of the present invention respectively for use.Experiment is carried out in 25ml zirconium still.3.73g methyl acetate, 4.56g iodomethane, 5.25g acetic acid, 0.3-0.4g lithium acetate and a certain amount of catalyst feed intake at every turn.Remove air in the still, fill CO to 4.1MPa, be warming up to 140 ℃, reacted 1 hour, be cooled to the pressure drop of room temperature record, cryosel water-bath cooling again in room temperature.Analyze the acetic anhydride growing amount with titration, relevant data and the results are shown in table 5.

Table 5. catalyst ligand and rhodium bonding type influence carbonylation system acetic anhydride catalytic activity

Catalyst	Rhodium concentration [Rh] mmol Rh/L	Carbonylation product increment mmol	Velocity constant k a L/mol/min	Velocity constant compares k/ks b
					8	2.81	15.3	2.83	1.33
8a	6.32	84	0.69	0.33

The a.k value calculating method is with table 2 footnote; B is with table 3, and promptly the velocity constant value with 1s is a standard of comparison.The result shows that both have marked difference to the catalytic activity of carbonylation.

Chelate 8a preparation method is as follows: the amino benzimidazole 0.2mmol of 2-and four carbonyl dichloros, two rhodium 39mg (0.1mmol), brium carbonate 60mg are placed 20ml methyl alcohol, and stirring and refluxing 6 hours, reactant liquor is transformed into dark brown gradually by initial reddish yellow.The pressure reducing and steaming solvent adds 1.0ml water and makes in the concentrate product crystallization complete, filter, with methanol-water mixture (v/v=5: 1) washing, drying, the crystalline powder of dark brown, infrared spectrum is at 2000-2100cm ^-1Two strong carbonylic stretching vibration absorption bands are arranged in the scope.

Claims (9)

1. multiple tooth heterodesmic mould assembly rhodium catalyst, it is characterized in that: catalyst is by multiple tooth heterodesmic mould assembly part and dicarbapentaborane diiodo-rhodium (I) anion [Rh (CO) ₂I ₂] ^-Formed have structure and be (A) or (A ')

Wherein: L ⁺Be the quaternary salt ion, R is alkyl or aryl, and L ° is free base; Rhodium accounts for total catalyst weight 0.5-25%, and the nitrogenous and phosphorus atoms sum of institute is 2-100 to the ratio of rhodium atom in multidentate ligand, and with L ⁺The nitrogen that form occurs, phosphorus group are 0.1-3 with the ratio that exists of the nitrogen that occurs with L ° of form, phosphorus, oxygen, methylthio group.

2. as the said multiple tooth heterodesmic mould assembly rhodium catalyst of claim 1, it is characterized in that in the described multiple tooth heterodesmic mould assembly part a plurality of L being arranged ⁺There are L ° of adjacent two part unit simultaneously with L ° of part unit L ⁺Or L °～L ⁺Between 1-9 the carbon atom of being separated by, on 1-9 carbon atom, can be connected with other carbon atom or alternate hetero atom be arranged, its main chain backbone connects with covalent bond.

3. as the said multiple tooth heterodesmic mould assembly rhodium catalyst of claim 2, it is characterized in that described covalent bond comprises aromatic gp, alicyclic ring key, singly-bound, two key and triple bond.

4. as the said multiple tooth heterodesmic mould assembly rhodium catalyst of claim 2, it is characterized in that described L ⁺With L ° be the multiple tooth organic or macromolecule ligand of nitrogenous, phosphorus, oxygen, sulphur.

5. as the said multiple tooth heterodesmic mould assembly rhodium catalyst of claim 1, it is characterized in that described L ° and L ⁺Connect and arrange in alternate mode, in abutting connection with L ⁺The L of part unit ° of part unit number is 1-3.

6. as the said multiple tooth heterodesmic mould assembly rhodium catalyst of claim 1, it is characterized in that described in multidentate ligand the nitrogenous and phosphorus atoms sum of institute be 5-30 to the ratio of rhodium atom.

7. as the said multiple tooth heterodesmic mould assembly rhodium catalyst of claim 1, rhodium (I) ionic complex that it is characterized in that having (A) or (A ') architectural feature includes following type:

2-amino-4-picoline type (1)

[Rh (CO) ₂I ₂] ^-Poly 2 vinyl pyridine type (2)

Tetramethylethylenediamine type (3)

[Rh (CO) ₂I ₂] ^-Poly N-vinyl imidazole type (4)

[Rh (CO) ₂I ₂] ^-4-vinylpyridine/methyl acrylate copolymer type (5)

[Rh (CO) ₂I ₂] ^-Poly 4 vinyl pyridine type (6) 2-mercaptobenzothiazole type (7)

[Rh (CO) ₂I ₂] ^-The amino benzimidazole type (8) of 2-

8. the method for making of a multiple tooth heterodesmic mould assembly rhodium catalyst is characterized in that:

(1) with multiple tooth organic compound, or multiple tooth macromolecular compound, or adopt by vinyl monomer through free radical initiation, solution or suspension polymerisation or copolymerization, or in polymerization or copolymerization vinyl monomer, add the multiple tooth macromolecular compound that diene or polyenoid class monomer obtain, join in the quaternary salt reagent iodomethane, or again with benzene, acetone or alcohols solvent dilution, stirring and refluxing reaction 0.5-24 hour, pressure reducing and steaming solvent or through suction filtration, washing, drying under reduced pressure obtains the part or all of quaternary salt part of multiple tooth organic compound and multiple tooth macromolecular compound; Or the quaternary salt part also can original position form in the carbonylation medium; Or the quaternary saltization of multiple tooth macromolecular compound is earlier vinyl monomer quaternary saltization nitrogenous, phosphorus to be made again crosslinked or linear multiple tooth macromolecular compound part;

(2) with above part and four carbonyl dihalo-s, two rhodium [Rh ₂(CO) ₄X ₂] content that accounts for 0.5-25wt% by rhodium in catalyst carries out proportioning, wherein X=I, Br or Cl, join in benzene or alcohols solvent or its mixed solvent, under room temperature and argon shield stirring reaction 0.5-4 hour, naturally dry or remove after filtration and desolvate, drying under reduced pressure just can obtain faint yellow to pale brown look even Dark grey particle or the multiple tooth heterodesmic mould assembly of crystalline powder rhodium (I) catalyst;

Or multiple tooth heterodesmic mould assembly rhodium (I) catalyst original position in reaction system forms, be about to precursor compound four carbonyl dihalo-s, two rhodiums or the three halogenation rhodium hydrates of multidentate ligand and rhodium, proportioning by the concentration 0.1-50mmol/L of rhodium in reaction system directly is added in the reaction medium, closed reactor, be pressed into CO, pressure is 0.3-6.0MPa, in intensification or course of reaction, just forms described multiple tooth heterodesmic mould assembly rhodium (I) catalyst automatically.

9. the purposes of a multiple tooth heterodesmic mould assembly rhodium catalyst is characterized in that multiple tooth heterodesmic mould assembly rhodium catalyst is used for carbonylation system acetic acid, methyl acetate or aceticanhydride.