Dmc complex-based catalyst and a method for preparation thereof

FIELD: polymerization catalysts.

SUBSTANCE: invention disclose a method for preparing catalyst based on DMC (4,4'-dichloro-α-methylbenzhydrol) appropriate to be used in polymerization of alkylene oxides into polyol-polyethers comprising following stages: (i) combining aqueous solution of metal salt with metal cyanide aqueous solution and allowing these solutions to interact, while at least one part of this reaction proceeds in presence of organic complexing agent to form dispersion of solid DMC-based complex in aqueous medium; (ii) combining dispersion obtained in stage (i) with essentially water-insoluble liquid capable of extracting solid DMC-based complex and thereby forming biphasic system consisting of first aqueous layer and a layer containing DMC-based complex and liquid added; (iii) removing first aqueous layer; and (iv) removing DMC-based complex from layer containing DMC-based catalyst.

EFFECT: lack of negative effect on DMC-based catalyst activity.

16 cl, 1 tbl, 3 ex

 

The present invention relates to a catalyst based on a complex cyanide with two metals and the method of its production.

Compounds of cyanide with two metals (DMC) are well-known catalysts for the polymerization of epoxy compounds, i.e. for the polymerization of alkalisation such as propylene oxide and ethylene oxide, to obtain polymers poly(alkalisation), also referred to as polyether polyols. The catalysts are highly active and produce the polyether polyols which have a low unsaturation compared with similar polyols obtained with the use of strongly basic catalysts such as potassium hydroxide. Conventional catalysts based on DMC (DMC catalysts) is produced by the interaction of aqueous solutions of metal salts and salts of cyanide metal with the formation of compounds DMC. In addition to the acquisition of polyether polyols, catalysts can be used to produce a variety of polymer products, including the polyol polyesters and polyols polyether and polyester. The polyols can be used to obtain polyurethanes by reacting them with polyisocyanates under appropriate conditions. Polyurethane products that can be obtained include polyurethane coatings, elastomers, hermit the key, foams and adhesives.

Catalysts based on DMC are usually obtained in the presence of organic complexing agent with a low molecular weight, usually, a simple ester, such as dimethoxyethane (glyme), or alcohol, such as tert-butyl alcohol. The complex forming agent has a positive effect on the activity of the catalyst for polymerization of epoxy compounds. Other known complexing agents include ketones, esters, amides and urea.

One traditional method of obtaining combined aqueous solutions of zinc chloride and hexacyanocobaltate potassium. The resulting precipitate hexacyanocobaltate zinc is combined with the organic complexing agent. This obtaining is often used excess metal salt. For example, in EP-A-555053 described method for the production of easily filterable catalysts based on DMC, where are controlled by the order of addition of reagents, the reaction temperature and the stoichiometric ratio of the reagents. In EP-A-555053 describes what should be used at least 100% stoichiometric excess of metal salt relative to the cyanide salt of the metal. In the working examples as the organic complexing agent is used dimethoxyethan. Catalysts based hexacyanocobaltate zinc obtained by the Y. these procedures, generally have a molar ratio of zinc chloride to hexacyanocobaltate zinc, about 0.6 or more.

Similarly, in EP-A-654302 describes a method for essentially amorphous catalysts based on DMC. These catalysts preferably are fabricated using the complexing agent based on water-soluble aliphatic alcohol, such as tert-butyl alcohol. In addition, for the manufacture of catalyst is used, the excess amount of metal salt. In this way it is essential that the salt of the metal salt of cyanide and metal complexing agent were uniformly mixed, for example, by mixing with a high shear or homogenization; conventional mechanical mixing is insufficient. Catalysts based hexacyanocobaltate zinc described in this document have more than 0.2 mol of metal salt per mole present hexacyanocobaltate zinc, usually more than 0.5 moles of metal salt per mole of hexacyanocobaltate zinc.

EP-A-755716 describes two different ways to obtain catalysts based on crystalline DMC complex. In one of the ways the catalyst is manufactured using excess metal salt, but the excess is less than 100% stoichiometric excess relative to the amount of salt is unida metal. The resulting catalyst contains less than about 0.2 moles of metal salt per mole of the compound DMC in the catalyst. The second method can be used in greater excess of metal salt, but the resulting catalyst is subsequently washed with a mixture of water and an organic complexing agent method, effective for the preparation of the catalyst on the basis of the DMC, which contains less than about 0.2 moles of metal salt per mole of the compound DMC in the catalyst.

In WO-A-97/40086 describes a method for catalysts on the basis of DMC, where aqueous solutions of excess salt metal salt and metal cyanide interact in the presence of organic complexing agent, using the effective mixing to form a slurry, combining the suspension with a simple polyester having a molecular weight less than 500, the selection of the catalyst, washing the catalyst with an aqueous solution containing additional organic complexing agent, and, finally, removing the solid catalyst based on the DMC. Suitable for use simple polyether is a polyether polyol such as polyethylene glycol. The final solid catalyst based on DMC contains 5-80% by weight. the polyether polyol.

In EP-A-700949 describes a method similar to the method of WO-A-97/40086, the difference lies in the fact that it is plain polyester (polyol)having a molecular weight of more than 500.

In discussing how the original system based on DMC is formed in the aqueous reaction medium. Used metal salts and salts formed during the reaction of formation of the complex, are well soluble in water and, therefore, will be present in the aqueous phase. As these salts, as a rule, have a deleterious effect on the catalyst activity on the basis of DMC, they must be removed before the catalyst based on DMC actually used to catalyze any reaction alkoxysilane. For example, assuming that zinc chloride is used as the metal salt, and hexacyanocobaltate potassium as a salt of the metal cyanide, unreacted zinc chloride and the potassium chloride formed in the reaction between zinc chloride and hexacyanocobaltate potassium will cause problems, because they have harmful effects on the activity of the final catalyst based on DMC. Therefore, these salts must be removed in quantitative terms to the extent possible, which is usually done with a selection of catalyst particles on the basis of the DMC from the aqueous phase.

All methods discussed so far have in common that the separation of the catalyst particles on the OS is ove DMC complex from the aqueous phase, containing salt, is quite difficult. For example, in the working examples of WO-A-97/40086 catalyst separation on the basis of the DMC complex from the aqueous phase comprises centrifuging and decanting, the techniques are not very practical when used on an industrial scale. The selection used in the examples of EP-A-55505, includes filtering using a centrifugal filter in a horizontal glass and filter media from easy nylon fabric. The selection of the formed catalyst particles on the basis of DMC in the working examples of EP-A-654302 includes either centrifugation or filtration, while in the examples of EP-A-755716 filtering is used. It will be understood that the filtering is also not optimal for use on an industrial scale, among other things, because of the problems of clogging of the filters, the occurrence of which is very likely. In addition, the technology Department to be used in the methods of the prior art discussed above, is likely to lead to the emergence of a quantity of water and, therefore, a certain amount of salt remaining in the product. This is undesirable.

The present invention provides a method of preparation of the catalyst based on the DMC, in which the selection of the formed catalyst particles on the core is ve DMC from the aqueous phase can be performed efficiently, smooth and clean on an industrial scale without any loss of catalytic activity. Accordingly, the method should produce a highly active catalyst based on DMC, or, in other words, the method according to the present invention should not adversely affect the activity of the catalyst based on DMC.

These and other objectives are achieved by the manner in which a particular liquid is added after the formation of the catalyst particles on the basis of DMC, this fluid promotes the separation of the phases, leading to the emergence of aqueous (lower) phase, containing salt, and a phase containing the catalyst pop-up on the surface of the aqueous phase.

Accordingly, the present invention relates to a method for producing a catalyst based on DMC, which involves the following stages:

(a) combining an aqueous solution of metal salt with the aqueous salt solution of the metal cyanide and the interaction of these solutions, while at least part of this reaction proceeds in the presence of organic complexing agent, thereby forming a dispersion of solid DMC complex in the aquatic environment;

(b) combining the dispersion obtained in stage (a)with a liquid which is essentially insoluble in water, and which can be extracted solid DMC complex formed in stage (a)of the water environment, and education is Finance when this two-phase system, consisting of the first water layer and the layer containing the DMC complex and added liquid;

(c) removing the first water layer; and

(d) extraction of the catalyst on the basis of the DMC from the layer containing the catalyst on the basis of the DMC.

At the stage of (a) an aqueous solution of metal salt is combined with an aqueous salt solution of a metal cyanide, and these solutions interact, while at least part of this reaction proceeds in the presence of organic complexing agent. Obtained after stage (a) the product is a dispersion of solid DMC complex in the aquatic environment. In General, the expression "aqueous medium"as it is used in this context, refers to water and to any additional substance (for example, complexing agent)dissolved in it.

Stage (a) may, accordingly, be carried out by stirring a solution of metal salt with the aqueous salt solution of a metal cyanide, while adding organic complexing agent or in a separate thread (for example, by itself or in a mixture with water)or in the form of a mixture with one or two streams of aqueous solutions of reagents, for example, dissolved in an aqueous solution of metal salt. In this mode of operation is finished, the reaction between the salt and metal cyanide salt of the metal takes place in the presence of an organic complex is forming agent. Alternatively, adding an organic complexing agent begins only after combining both streams of aqueous solutions of reagents. Organic complexing agent may appropriately be added by itself or in a mixture with water. In this operating mode, the complexing agent will be present only during part of the reaction between these two streams of reagents. Namely, as soon as the salt of the metal salt and metal cyanide will come into contact, will begin the formation of the DMC. This can be seen as an immediate precipitate at the beginning of adding one stream of reactant to another. Thus, when adding the organic complexing agent is only the beginning, immediately after the reunification of the amount of the metal salt solution and the salt solution of the metal cyanide, the formation of the complex DMC has already happened. For the purposes of the present invention, as detected, is very useful when the complexing agent is added directly after the unification of the salt solution of the metal salt solution of the metal cyanide.

Suitable metal salts and salts of cyanide metals are described, for example, in EP-A-755716. Thus, suitable metal salts are, accordingly, water-soluble salts having the formula M(X nin which M is chosen from the group consisting of Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), AI(III), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II) and Cr(III). More preferably, M is selected from the group consisting of Zn(II), Fe(II), Co (II) and Ni(II). In this formula, X preferably represents an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate. The value of n corresponds to the valence state of M, and usually from 1 to 3. Examples of suitable metal salts include, but are not limited to, zinc chloride, zinc bromide, zinc acetate, acetylated zinc, zinc benzoate, zinc nitrate, chloride, iron (II)sulfate iron (II)bromide, iron (II)chloride cobalt (II)thiocyanate, cobalt (II)formate, Nickel (II)nitrate, Nickel (II), and the like, and mixtures thereof. The halides of zinc, and, in particular, zinc chloride, are preferred.

Salt cyanide metal is a water-soluble salt of a metal cyanide, preferably having the General formula (Y)aM’(CN)b(A)within which M’ is chosen from the group consisting of Fe(II), Fe(III), Co(II), Co(III), Cr(II)Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V). More preferably, M’ is chosen from the group consisting of Co (II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II). Water-soluble salt of the metal cyanide may contain about the Jn or more of these metals. In this formula, Y represents an alkali metal ion or alkali earth metal ion such as lithium, sodium, potassium and calcium. And represents an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate. As "a"and "b"are integers more than or equal to 1; "C" can be 0 or an integer; the amount of charges a, b and C is equal to the charge of M’. Suitable water-soluble cyanide salt of the metal include, for example, hexacyanocobaltate(III), potassium hexacyanoferrate(II) potassium hexacyanoferrate(III) potassium hexacyanocobaltate(III) calcium and hexacyanoferrate(III) lithium.

Used organic complexing agent should be, as a rule, moderately soluble in water. Suitable complexing agents, for example, described in EP-A-555053 and, as a rule, are water-soluble organic compounds containing a heteroatom, which may form a complex with the compound of cyanide with the two metals. Thus, suitable complexing agents include alcohols, aldehydes, ketones, ethers, esters, amides, urea, NITRILES, sulfides and mixtures thereof. Preferred complexing agents are ethers, such dimethoxyethane and diglyme, and vodorastvorimye aliphatic alcohols, such as ethanol, isopropyl alcohol, n-butyl alcohol (1-butanol), isobutyl alcohol (2-methyl-1-propanol), sec-butyl alcohol (2-butanol) and tert-butyl alcohol (2-methyl-2-propanol). Among them dimethoxyethane and tert-butyl alcohol are most preferred.

Merging both threads aqueous reagents can be carried out using conventional mixing technologies, including mechanical stirring and ultrasonic agitation. Although their use and may not be required to use technology homogeneous mixing such as stirring with a high shear or homogenization. The interaction between the salt and metal cyanide salt of the metal may be carried out at a pressure of from 0.5 to 10 bar and at temperatures from 0 to 80°C. However, it is preferable that the interaction was carried out under mild conditions, i.e. at a pressure of 0.5 to 2 bar and at a temperature of from 10 to 40°C.

After flowing interaction and produces compound DMC, to the reaction product of stage (a) is added to the extracting liquid. Typically, extracting liquid is added with stirring, and the stirring continues until the liquid is evenly distributed throughout the reaction mixture. The time of mixing is not critical and can be from 10 seconds up to 2 hours. With the economy the economic point of view, it is considered useful for a method to maintain the mixing time as short as possible, and therefore, the mixing time will generally be from 30 seconds to 30 minutes

After the stirring is stopped, the reaction mixture provide sufficient time to defend, that is sufficient time for separation into two phases: the aqueous bottom layer and the layer pop-up above it, containing a catalyst based on DMC, dispersed in the extracting liquid.

The number of added extracting fluid should be sufficient to effect the separation of the phases. Accordingly, it is at least 1 wt.%, preferably at least 2 wt.%, and more preferably at least 3 wt.%. respect to the total mass of the reaction product of stage (a), extracting liquid. Can be used any number of the extracting fluid is greater than the minimum number required for the implementation of phase separation. The maximum amount is usually determined by the hardware limitations, for example, the volume of the reactor. Typically, however, the number of added extracting solvent not to exceed 50 wt.%, preferably, 30 wt.%, and more preferably, 20 wt.%. respect to the total mass of the reaction product of stage (a). To the providing preferably carried out at temperatures from 0 to 80° With, suitably from 10 to 50°C. the Pressure may be the same as during the reaction stage (a).

Suitable extracting fluid used in stage (b)must, in essence, to meet two requirements: first, they must be essentially insoluble in water, and second, they must be able to extract the DMC complex from the aqueous phase. The latter requirement implies that the organic complexing. the agent should have the advantage of interacting with this extracting liquid in front of an aqueous phase containing dissolved salts. Namely, it is assumed that the complexing agent interacts with the extracting liquid and, in fact, is displaced together with the DMC complex from the aqueous phase in the phase formed extracting liquid. Extracting liquid may, for example, be a complex ether, a ketone, a simple ester, complex fluids, alcohol, dispertab, (di)allylcarbamate, nitrile or alkanol.

Preferably used extracting liquid contains a compound of General formula (I):

where:

R1represents hydrogen, aryl group, substituted or unsubstituted C1-C10alkyl group or the group R3-NH-,

R2represents hydrogen, optionally halogenerator the 1-C10alkyl group, a group R3-NH-, group -, R-C(O)O-R5group-R4-OH, or a cyanide group,

R3represents hydrogen or C1-C10alkyl group,

R4represents a substituted or unsubstituted alkylenes group having 2-15 carbon atoms,

R5represents hydrogen, substituted or unsubstituted C1-C10alkyl group, and

n and m independently are 0 or 1.

In the first preferred embodiment, in the General formula (I), R1represents hydrogen, m=1, n=0, and R2represents a group-R4-OH, where R4represents alkylenes group having 3-10 carbon atoms. A specific example of this preferred compounds include 2-butyl-2-ethyl-1,3-propandiol.

In the second preferred embodiment of the present invention, in the General formula (I), R1and R2independently represent an alkyl group having 1-5 carbon atoms, m=1 and n=0. Preferred examples of this embodiment are diethyl simple ether, methyl tert-butyl simple ether, diisopropyl simple ether and disutility simple ether. Of these methyl tert-butyl simple ether is especially preferred.

In the third preferred embodiment, in the General formula (I), R1represents al the ilen group, having 1-6 carbon atoms, m=1, n=1, and R2represents a hydrogen or alkyl group having 1-6 carbon atoms, or a group-R4-C (O)O-R5where R4represents a substituted or unsubstituted alkylenes group having 3-15 carbon atoms, and where R5represents an alkyl group having 1-5 carbon atoms. The group R4can contain alicyclic, aliphatic (alkyl) or polar substituents, such1-C4alkoxygroup. Accordingly, R4represents a 1,3-propylene group with one or two substituents on the middle carbon atom. Preferred examples of this embodiment are ethyl formate, ethyl acetate, ethyl-2-ethyl-3-methylbutanoate, diethylmalonate and diethyl-2-cyclohexyl-2-propylmalonate.

In another preferred embodiment of General formula (I), R1and R2independently represent an alkyl group having 1-5 carbon atoms, m=0 and n=0. Thus, in this embodiment the connection is added in stage (b)is an alkane having from 2 to 10 carbon atoms. Heptane, as found, is particularly suitable for the purposes of the present invention.

In the preferred embodiment of General formula (I), R1represents an aryl group, eligible, phenyl group, or alkyl group having the General 1-5 carbon atoms, R2is a cyanide group, m=0 and n=0. Preferred examples of this embodiment are benzonitrile and mevalonate (tert-butylnitrite).

In a preferred embodiment, R1and R2independently represent a group R3-NH-, where R3represents hydrogen or C1-C10alkyl group, m=0 and n=1. Preferred examples of this embodiment are BUTYLCARBAMATE, dibutylsebacate and propylgallate.

In a preferred embodiment, R1represents hydrogen, R2represents a halogen-substituted C1-C5alkyl group, m=0 and n=0. Preferred examples of this embodiment are dichloromethane, 1,2-dichloroethane and tetrachlorethane.

At the stage (C) of the method according to the present invention, the resulting aqueous layer was removed. Since the water layer forms a bottom layer formed of a two-phase system, it can be easily carried out, for example, using drainage water layer through a valve at the bottom of the tank, in which the separation of the phases. Besides water, the aqueous layer typically will contain an excess of used complexing agent (i.e., the amount of complexing agent, which has not acceded to the complex DMC), a water-soluble salt, such unreacted metal salt (e.g. the R, zinc chloride), and any water-soluble salt formed during the interaction between the salt and metal cyanide salt of a metal (e.g. potassium chloride and cobalt salts), and possibly a small amount of extracting compounds remaining in the aqueous phase. Typically, the remote water layer will be from 10 to 90% of the total volume of liquid plus catalyst particles present in the tank, but the volume ratio of the aqueous layer to a layer extracting compounds is not critical to use of the present invention. The exact relationship, as a rule, is determined by hardware limitations. After removal of the aqueous phase remaining phase contains solid particles of the catalyst on the basis of the DMC, which are dispersed or distributed in the form of fine particles in extracting the connection and subsequently retrieved in stage (d).

Phase extraction (d) can be done in different ways. As described in descriptions of the patents discussed above, this extraction procedure, as a rule, will include the mixing of the catalyst based on DMC with a complexing agent, optionally in mixture with water, and re-separation of the catalyst based on DMC and complexing agent/water, for example, by filtration, centrifugation/desantirovaniya or rapid evaporation. This item is ocedure may be repeated one or more times. Ultimately, the catalyst is dried and extracted in the form of solids. As described in WO-A-97/40086 and EP-A-700949, the final solid catalyst may also be extracted in the form of a composition comprising 5-80 wt.%. polyether having a molecular weight of, respectively, less than 500, and more than 500. Stage (d) under this method suitably includes adding water/complexing agent to the layer of catalyst on the basis of the DMC and the mixing of the catalyst layer and water/complexing agent (e.g., by stirring), the formation of a two-phase system and remove the water layer. This procedure can be repeated one to five times, after which the remaining layer of the catalyst may be dried and the catalyst may be recovered in solid form (powder form) or, alternatively, to a layer of catalyst can be added to a liquid polyether polyol, and the formed suspension of the catalyst in the polyol polyether, which can be used as such.

In one of the embodiments, the preferred phase extraction (d) contains stage

(d1) mixing the organic complexing agent, water and, optionally, additional extracting liquid from a layer containing a catalyst based on DMC, and education in this two-phase system consisting of the second water slaai layer, containing the catalyst on the basis of the DMC;

(d2) removing the second water layer;

(d3) optional repeating steps (d1) and (d2) from one to five times, suitably, one or two times;

(d4) adding an organic complexing agent to a layer containing a catalyst based on DMC, during mixing; and

(d5) removing complexing agent (for example, by rapid evaporation or distillation, and extraction of the catalyst based on DMC in the form of solid particles.

In another embodiment, the phase extraction (d) includes a stage (d1)-(d4), as defined above, with the subsequent:

(d5) adding a liquid polyol to the product stage (d4), with formation of a suspension of catalyst based on DMC in liquid polyol/organic complexing agent;

(d6) removing the organic complexing agent;

and

(d7) removing the catalyst based on DMC in suspension in a liquid polyol.

The amount of water used on stage (d1), should be sufficient for the formation of a water layer. Organic complexing agent and water and, optionally, additional extracting liquid can be added as separate streams or as a mixture in a single thread. Additional extracting liquid can be added to compensate for any small amount, ostaszewo the I in the liquid phase. If it is added, in small quantities. The mass ratio of complexing agent to the water suitably is in the range from 5:95 to 50:50, more preferably from 10:90 to 40:60. The total amount of water and added complexing agent is not critical and may, for example, to match the number by 20%. more or less than the number of the aqueous layer removed at the stage (C). Water and complexing agent is effectively mixed with the layer of catalyst on the basis of the DMC, for example, by mechanical mixing. Once there is an effective stirring, the obtained mixture is allowed the opportunity to settle with the fact that two-phase system could be formed. Once this occurs, the aqueous (bottom) layer is removed at the stage (d2). This can happen in the same way as described above for stage (C). The procedure can be repeated one to five times, preferably once or twice.

On stage (d4) of pure organic complexing agent is added to a layer of catalyst on the basis of DMC under stirring in an amount which corresponds to the number of the aqueous layer removed at the previous stage, although the number is 20%. more or less will still be acceptable.

At the next stage (d5), the complexing agent may be removed by distillation or rapid evaporation, is so removing the catalyst based on DMC in the form of solids. The complexing agent may be, for example, quickly evaporated under atmospheric conditions or under reduced pressure. Rapid evaporation under reduced pressure is preferred because it makes it possible for separation at a lower temperature, which reduces the risk of thermal decomposition of the catalyst based on DMC. In the preferred embodiment, the organic complexing agent is removed by rapid evaporation under vacuum at a temperature of 50-80°C. Together with the complexing agent also removes traces of water and extracting the liquid, which are still present in the mixture. The catalyst based on DMC is extracted in the form of solids and can be further processed by drying.

Alternatively, stage (d5) includes adding a polyol in a quantity sufficient to form a suspension of catalyst based on DMC in liquid polyol and a complexing agent. Preferably, the amount of polyol is such that the solids content in the resulting suspension is 1-50 wt.%, more preferably 1-30 wt.%, and most preferably 1-10% wt.

Added polyol may be any liquid polyol that is suitable as a liquid medium for cha the TIC-based catalyst DMC. In this application of the catalyst based on the DMC - catalyzed polymerization of alkalisation in polyols polyether is preferable to use a polyol, which is compatible with the polyether polyols, which must be received and which will not have any negative impact on the final polyol polyether, when present in trace quantities. Therefore, it is particularly preferred to use polyether polyol such as polyether polyol, which should be obtained by using a catalyst based on DMC. Examples of suitable polyols, thus, include polyols such as polyethylene glycol, but the preferred polyols are poly(alkylenes), polyols based on propylene oxide and/or ethylene oxide, such as those that are intended to obtain by using a catalyst based on DMC.

At a later stage (d6) organic complexing agent is removed from the slurry catalyst. This can be accomplished by any means known in the field as suitable for the separation of liquid-liquid. The preferred method for the purpose of the present invention is the rapid evaporation of the complexing agent at atmospheric conditions or the ri reduced pressure. Rapid evaporation under reduced pressure is preferred because it makes it possible for separation at a lower temperature, which reduces the risk of thermal decomposition of the catalyst based on DMC. In a particularly preferred embodiment, the organic complexing agent is removed by rapid evaporation under vacuum at a temperature of 50-80°C. Together with the complexing agent also removes traces of water and extracting the liquid, which are still present in the mixture.

Finally, at the stage (d7), the catalyst based on DMC is recovered in the form of a suspension in the polyol. The advantage of this suspension is that it is stable during storage and can, for example, be stored in the drum. Moreover, the dosing of the catalyst and its distribution in the environment of polymerization is greatly simplified by the use of a suspension of the catalyst.

In an additional aspect, the present invention also relates to the catalyst obtained by the method as described above.

In this latter aspect, the present invention also relates to a method of polymerization of accelerated, including polymerization accelerated in the presence of a catalyst based on DMC and initiator containing a hydroxyl group. The preferred acceleratedly are ethylene oxide, propylene oxide, budenoside,stimulated, and the like, and mixtures thereof. The method can be used to produce homopolymers, random copolymers or block copolymers.

Catalysts based on DMC according to the present invention are very active and, therefore, demonstrate a high polymerization rate. They are active enough to allow their use at very low concentrations, such as 25 ppm or less. At such low concentrations, the catalyst can often remain in the polyether polyol without harmful effects on the quality of the product. The ability to leave the catalyst in the polyol is an important advantage, because at the present time commercial polyols require a stage of removal of the catalyst.

The polyol polyesters obtained by using a catalyst based on DMC, prepared in accordance with the present invention have a very low unsaturation, namely considerably smaller than about to 0.007 mEq/g, or even less than 0.005 mEq/g Such low unsaturation provides a number of advantages polyurethanes obtained by using polyols of the present invention.

The polyol polyesters obtained by using the catalysts of the present invention preferably have a nominal average functionality of from 2 to 8, more preferably from 2 to 6. The polyols which may be srednekamennogo molecular weight of up to 50000, but, as a rule, the molecular weight is in the range from 500 to 12,000, more typically, from 2000 to 8000.

The present invention is additionally illustrated by the following examples, but without limiting the present invention to these specific embodiments.

Example 1. Obtaining catalyst based on DMC

Procedure A. an Aqueous solution of zinc chloride (30 g in 100 ml water) is added to one litre glass reactor, equipped with a mechanical stirrer. An aqueous solution of hexacyanocobaltate potassium (12 g in 225 ml of water) is added under stirring within 30 minutes Directly after adding all hexacyanocobaltate potassium, with stirring, add a mixture of water (95 g) and tert-butyl alcohol (117 g). Stirring is continued for another 30 min and the mixture allow to stand overnight to obtain a viscous white stable dispersion of particles of the complex on the basis of DMC in the phase of water/tert-butyl alcohol.

Procedure Century To the dispersion obtained after the procedure And, under stirring, add methyl tert-butyl simple ether (70 g). Stirring is continued for another 5 minutes After cessation of mixing are formed of two separate layers: a very viscous white top layer and a transparent aqueous bottom layer. After drainage of the lower layer (337 g) added with stirring 337 g 25/75 m/MSMEs tert-butyl alcohol/water. After stirring for an additional 5 min, followed by settling for 30 minutes, a transparent bottom layer, drain again. This layer has a lot 355, Then 355 g 25/75 W/W mixture of tert-butyl alcohol and water is added under stirring together with 15 g of methyl tert-butyl simple ether. After stirring for an additional 5 min, followed by settling for 30 minutes, a transparent bottom layer drain again. Drained layer has a weight of 308, Then added with stirring 308 g of tert-butyl alcohol, and then 240 g propyleneoxide adduct of glycerine having srednekamennogo molecular weight of 670 daltons (G670). After stirring for an additional 30 min. tert-butyl alcohol and the remainder water is removed by distillation under reduced pressure (300 mbar) at 60°up until the water content in the mixture of DMC/G670 will not become less than 0.5% wt.

The product is a very viscous stable dispersion of white color containing 5% wt. catalyst particles on the basis of DMC dispersed in G670.

Example 2. Getting polyol

One litre reactor with mechanical stirring is loaded 89 g G670 and 160 mg of dispersion of the catalyst on the basis of DMC, obtained in example 1 (corresponding to 20 ppm of DMC catalyst with respect to the final product). Traces of water are removed by heating the obtained R is the result of the mixture to 130° With 5 mbar. The pressure is then lowered to 50 mbar with nitrogen, after which the propylene oxide added to until the pressure becomes equal to 1.1 bar (corresponding to 6 g of propylene oxide). Then add the remaining 305 g of propylene oxide, while maintaining the pressure at 1.1 bar. After adding all of propylene, the reaction mixture is kept at 130°until then, until the pressure reaches a constant value.

Reactivity is defined as the time required for conversion of propoxylate G670 in polyol with molecular weight of 3000 (G3000), at 130°and at a pressure of propylene oxide 1.1 bar, with 20 ppm of catalyst (with respect to the final product).

Reactivity in this example was 91 minutes

Comparative example 1

Example 1 is repeated, except that the viscous white stable dispersion of particles of the complex on the basis of DMC in the phase of water/tert-butyl alcohol obtained after the procedure And is not subject extraction processing (procedure), as described in example 1, but instead is processed by centrifugation (500 rpm 4800 G) for 1.5 hour, followed by decanting. The resulting pellet catalyst was then re-suspended in a mixture of tert-butyl alcohol/water (70/30 mass/mass) and centrifuged, and again decanted. Sediment re WM is androuet in pure tert-butyl alcohol, centrifuged and decanted.

Finally, the resulting material was re-suspended in the number G670 in excess of its quantity in 19 times. After stirring for an additional 30 min, tert-butyl alcohol and the remainder water are removed by distillation under reduced pressure (300 mbar)at 60°up until the water content in the mixture of DMC/G670 will not become less than 0.5% wt.

The product is a very viscous stable dispersion of white color containing 5% wt. catalyst particles on the basis of DMC dispersed in G670.

The method used in this comparative example, is rather time-consuming, especially decanting and filtering are unsuitable for use in commercial scale.

Comparative example 2

Example 2 is repeated, but using dispersion of the catalyst on the basis of DMC from comparative example 1. Reactivity was 109 minutes

When mapped to example 2 with comparative example 2, it can be seen that a catalyst based on DMC the present invention, as shown in example 1, leads to the catalyst on the basis of the DMC, which is even better than the catalyst based on DMC, obtained in the usual way, as shown in comparative example 1. Accordingly, the method according to the present invention includes a stage that can be applied in Promyshlenno scale (as opposed to treatments desantirovaniya and filtering, illustrated in comparative example 1), resulting in an excellent catalyst.

Example 3. Extracting liquid

In each experiment, listed below a certain amount extracting liquid added to the water dispersion obtained in example 1, procedure A, at room temperature. The number of added extracting solvent is 5, 10, 15 or 20% wt. in relation to the total weight of the aqueous dispersion to which they are added.

Examine at what number is the separation of the phases with the release of DMC complex from the aqueous phase into the phase of extracting liquid. The number, which is the separation of the phases at room temperature, is indicated in the table. When phase separation occurs at a different temperature, it is indicated separately.

From the table we can see that several different compounds are suitable extracting liquids for use in the method of preparation of the catalyst based on the DMC according to the present invention.

Extracting fluid
Etc.Extracting liquidThe separation of the phases
1Dichloromethane10% (5% at 40°)
2Butyl-2-ethyl-1,3-propandiol 5%
3Diethyl simple ether10%
4The tert-butyl simple ether10% (5% at 40°)
5Tert-amylotrophic simple ether5%
6Di-isopropyl simple ether5%
7Heptane10% (5% at 40°)
8Benzonitrile5%
9Pilonidal5%
10Ethyl formate20%
11The ethyl acetate15%
12Ethyl 2-ethyl-C-methylbutanoate5%
13BUTYLCARBAMATE10%

1. The method of obtaining dual metallocyanide (DMC) catalyst, which includes stages

(a) combining an aqueous solution of metal salt with the aqueous salt solution of the metal cyanide and the interaction of these solutions, where at least part of this interaction takes place in the presence of organic complexing agent, thereby forming a dispersion of solid DMC complex in the aquatic environment;

(b) combining the dispersion obtained in stage (a), with a liquid, which is, essentially, not rastvorimyv water and which can be extracted solid DMC complex, formed in stage (a)of the water environment, and education in this two-phase system consisting of the first water layer and the layer containing the DMC complex and added liquid;

(c) removing the first water layer and

(d) extracting DMC-catalyst layer containing the DMC catalyst.

2. The method according to claim 1, wherein the organic complexing agent is a tert-butyl alcohol or dimethoxyethane.

3. The method according to claim 1 or 2, wherein the liquid includes a compound of General formula (I)

where R1represents hydrogen, aryl group, substituted or unsubstituted With1-C10alkyl group or the group R3-NH-,

R2represents hydrogen, optionally halogenated C1-C10alkyl group, a group R3-NH-, group -, R4-C(O)O-R5or cyanide group,

R3represents hydrogen or C1-C10alkyl group,

R4represents a substituted or unsubstituted alkylenes group having 2-15 carbon atoms,

R5represents hydrogen, substituted or unsubstituted C1-C10alkyl group,

N and m independently are 0 or 1.

4. The method according to claim 1 or 2, wherein the liquid includes a compound of General f is rmula (I)

where R1represents hydrogen, m=1, n=0 and R2represents a group-R4-OH, where R4represents alkylenes group having 3-10 carbon atoms.

5. The method according to claim 3, in which in the General formula (I) R1and R2independently represent an alkyl group having 1-5 carbon atoms, m=1 and n=0.

6. The method according to claim 5, in which the compound of General formula (I) is selected from diethyl simple ether, methyl tert-butyl simple ether, diisopropyl simple ether and dibutylamino simple ether.

7. The method according to claim 3, in which in the General formula (I) R1represents an alkyl group having 1-6 carbon atoms, m=1, n=1, and R2represents a hydrogen or alkyl group having 1-6 carbon atoms, or a group-R4-C(O)O-R5where R4represents a substituted or unsubstituted alkylenes group having 3-15 carbon atoms, and R5represents an alkyl group having 1-5 carbon atoms.

8. The method according to claim 7, in which the compound of General formula (I) are chosen from ethylformate, ethyl acetate, ethyl-2-ethyl-3-methylbutanoate, diethylmalonate and diethyl-2-cyclohexyl-2-propylmalonate.

9. The method according to claim 3, in which in the General formula (I) R1and R2independently represent an alkyl group having 1-5 atom is in carbon, m=0 and n=0.

10. The method according to claim 3, in which in the General formula (I) R1represents an aryl group or alkyl group having 1-5 carbon atoms, R2is a cyanide group, m=0 and n=0.

11. The method according to claim 3, in which in the General formula (I) R1and R2independently represent a group R3-NH-, where R3represents hydrogen or C1-C10alkyl group, m=0 and n=1.

12. The method according to claim 3, in which in the General formula (I) R1represents hydrogen, R2represents a halogen-substituted C1-C5alkyl group, m=0 and n=0.

13. The method according to any one of claims 1 to 12, in which stage (d) includes stages

(d1) mixing the organic complexing agent and water with a layer containing the DMC catalyst, and education in this two-phase system consisting of the second water layer and the layer containing the DMC catalyst;

(d2) removing the second water layer;

(d3) optional repeating steps (d1) and (d2) from one to five times;

(d4) adding an organic complexing agent to the layer containing the DMC catalyst, with stirring and

(d5) removing complexing agent and retrieve DMC-catalyst in the form of solid particles.

14. The method according to any one of claims 1 to 12, in which stage (d) includes stages

(d1) mixing of the organic complexing agent and water with a layer, containing DMC catalyst, and education in this two-phase system consisting of the second water layer and the layer containing the DMC catalyst;

(d2) removing the second water layer;

(d3) optional repeating steps (d1) and (d2) from one to five times;

(d4) adding an organic complexing agent to the layer containing the DMC catalyst, with stirring;

(d5) adding a liquid polyol to the product from step (d4), forming a suspension DMC-catalyst in a liquid medium polyol/organic complexing agent;

(d6) removal of the organic complexing agent and

(d7) extract DMC-catalyst in suspension in a liquid polyol.

15. The catalyst obtained by the method according to any one of claims 1 to 14.

16. The method of polymerization of alkalisation, including polymerization accelerated in the presence of the DMC catalyst according to § 15 and initiator containing a hydroxyl group.



 

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The invention relates to methods of producing double metallocyanide (DМС) catalysts for the polymerization of epoxy compounds

The invention relates to an improved dual metallocyanide (DMC) catalysts and methods for their preparation

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20 cl, 10 ex, 12 tbl, 10 dwg

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71 cl, 99 ex, 13 tbl

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11 cl, 1 tbl, 45 ex

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2 cl, 1 tbl, 11 ex

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3 cl, 2 tbl, 18 ex

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8 cl, 1 dwg, 11 ex

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40 cl, 2 tbl, 19 ex

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4 cl, 1 tbl, 8 ex

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5 cl, 1 tbl, 16 ex

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