The method of receiving polyoxyethyleneglycol with low levels of transition metals using dual metallocyanide complex catalyst

 

(57) Abstract:

Describes a method of obtaining substantially free of transition metals polyether-based polyoxyalkylene with terminal hydroxyl functional groups by oxyalkylene containing one or more substituted hydrogen atoms oxyalkylene initiation of a molecule or molecules of one or more oxide alkylene and polymerization in the presence of double metallocyanide complex catalyst oxyalkylene with subsequent regeneration is substantially free of transition metals polyether-based polyoxyalkylene with terminal hydroxyl functional groups; however, for a given catalyst, the polymerization rate of oxide alkylene defined relative to the oxypropylation with propylene oxide, is greater or equal to approximately 5 g of propylene oxide/min at 105oC, at a pressure of propylene oxide to 0.68 bar and content of 100 ppm catalyst, based on weight of polyether-based polyoxypropylene where the concentration mentioned double metallocyanide catalyst in the process mentioned by oxyalkylation is kilena with terminal hydroxyl functional groups. The technical result is simplification. 3 S. and 12 C. p. F.-ly, 1 table. , 1 Il.

The invention relates to a method of obtaining polyoxyethyleneglycol with extremely low content of transition metal ions by catalyzed double metallocyanide complex polyoxyalkylene corresponding hydrogen initiator in the presence of 15 or less parts per million (ppm) double metallocyanide complex catalyst. Formed polyoxyalkylene contain commercially acceptable levels of transition metal ions without the need for additional filtering and/or cleaning that was practiced before using these catalysts.

Background of the invention

Polyoxyalkylene, in particular polyols having two or more functional groups, are the basis for the polyurethane industry, because react with di - and polyisocyanates with the formation of numerous polyurethane and poliuretanovykh products, including flexible and rigid polyurethane foams, microporous and deprived then elastomers. Such polyoxyalkylene previously received, in General, the polymerization of the oxide alkylene, obysnogo catalyst, for example sodium hydroxide or potassium, or of the corresponding alkoxides.

In 60-70-ies for oxypropylation began to use double metallocyanide complex (DMC) catalysts. Found that these catalysts, for example, non-stoichiometric complex of hexacyanocobaltate zinc - diglyme, are extremely effective for oxypropylation in certain conditions. You could get polyethers with terminal hydroxyl groups of a much larger molecular weight than previously. In the case of Polyoxypropylenediamine with equivalent mass of about 2000 daltons was achieved levels of unsaturation within 0,015-0,020 IEC/g compared to 0,07-0,09 IEC/g u similar in other respects polyols, catalyzed by base. Much greater cost of these DMC complex catalyst compared to sodium hydroxide and potassium prevented them from commercialization, even though they were more active than the conventional basic catalysts. Moreover, the presence of significant quantities of transition metals, in particular zinc and cobalt in the original polyoxyalkylene product required a costly and time-consuming purification methods. Even today, many who="ptx2">

In the 80's and early 90-ies were released DMC complex catalyst possessing a significantly higher catalytic activity compared with previous catalysts. Similar to the DMC complex catalyst, for example, described in U.S. patent N 5.158.922, could be used in concentrations of approximately 250-500 ppm, based on the weight polyol as one product. Due to the increased activity value of the catalyst per se has become competitive with the cost of traditional main catalysts of polyoxyethyleneglycol. Again, however, the cost and difficulty of removing residual catalyst from the product prevented wide-scale commercialization.

Recently the owner of the present invention has developed DMC complex catalyst is much more active. As a result of this new opportunity to reduce levels below catalysts previously practiced ranges 250-500 ppm to 100 ppm, with maintaining an acceptable reaction rate. The catalytic activity of these new catalysts is so high that the duration of the process, in General, limited cooling capabilities of the reactor to polyoxyalkylene, not speed pokazalosi getting polyoxyethyleneglycol using the DMC complex catalyst, despite the fact that it preserved the need for cleaning products polyol as one to remove residual complex of transition metals used as catalysts. The stage of purification, until that an undesirable increase the duration of the process.

Polyoxyalkylene obtained using these exceptionally active (EA) DMC complex catalysts have several unusual characteristics, which can advantageously be used for the preparation of formulations of new polyurethanes, etc. first, the degree of unsaturation is extremely low and is generally from 0.002 to approximately 0,007 IEC/g in contrast to the levels of unsaturation (of 0.015-0.018 IEC/g) of polyoxyethyleneglycol obtained using DMC catalysts, such as those described in U.S. patent N 5.158.922. Moreover, polyethers with terminal hydroxyl groups obtained with the previously used DMC complex catalyst, which included typically 5-10% of a component with a low molecular weight, considered monofunctional unsaturated species, while helpanimals chromatography of polyoxyethyleneglycol obtained by EA-DMC catalysts have not found any substantial code unsaturation. Polyoxyalkylene obtained with these more active DMC catalysts, also demonstrate a very narrow molecular weight distribution. Actually ever get the polydispersity (MW/Mn) less 1,30; polydispersity vast majority of polyoxyethyleneglycol obtained using the catalysts of the third generation, is 1.07-1.15 or less. Polyoxyalkylene are essentially monodisperse.

The use of smaller quantities of DMC catalysts would certainly be preferable. However, at very low levels of catalysts, for example in the range 25 to less than 100 ppm, there are several problems. First, it is a serious concern deactivation of the catalysts. It is known that several common types of bases, such as sodium hydroxide, potassium hydroxide, etc. are effective catalytic poisons for DMC complex catalyst. Negligibly small amounts of these ingredients may not play a role in the case of very large quantities of catalyst, for example 250-500 ppm, however in case of minor quantities of catalysts even small amounts of catalytic poisons can lead to full a catalyst in contrast to the polymerization activity. So, I guess impossible to use the content of the catalyst is significantly below 100 ppm.

DMC complex catalysts are also characterized by an initial latent period, when after adding oxide alkylene in the polymerization reactor is delayed for a significant period of time, the so-called "induction period", during which the polymerization is not actually happening. On completion of the induction period can be indicated by a sharp pressure drop in the reactor after adding the initial amount of oxide alkylene. After activation of the catalyst, the polymerization proceeds quite quickly. An inverse correlation between the duration of the induction period and the used amount of the catalyst, although this dependence is not linear. In some cases, over a long induction periods were followed by inactivation of the catalyst. Additional undesirable effects of extremely low levels of catalyst is undesirable increase polydispersity polyol as one product and a concomitant increase in viscosity. In General, the desirable products of low viscosity, and for many applications of gelatinesilberprint with extremely low levels, for example, 15 ppm or less DMC complex catalyst. It would be desirable, then, to get the way in which the amount of catalyst is so low that it can be left in plain polyester with terminal hydroxyl groups, without cleaning or other methods for removal of transition metals. In addition, it would be desirable to obtain a method that provides polyoxyalkylene exceptionally low polydispersity and low viscosity with low levels DMC complex catalyst.

The invention

Unexpectedly, it was found that polyoxyalkylene very narrow polydispersity and low viscosity can be obtained even when the levels DMC complex catalyst 15 ppm or less, if the catalyst oxyalkylene used DMC complex catalyst having a rate of polymerization of propylene oxide (PO) above 5 g PO/100 ppm of catalyst at 105oC (EA-DMC catalysts). Unexpectedly also found that the polyols of low polydispersity and low viscosity can be obtained in the case when the polymerization reaction is carried out at a temperature that exceeds the normal temperature oxyalkylene. Cootvetctvuuschix characteristics of products, obtained with higher levels of catalysts under conventional temperatures oxyalkylene. The amount of catalysts used in the process, so low that it does not need to be cleaned and at the same time it is below the generally accepted standards for transition metals in the polyol as one product. The use of high temperatures oxyalkylene and/or use of master batches previously initiated by the initiator/oxide alkylene/catalyst significantly reduces the duration of the induction period associated with the DMC complex catalyst.

A brief description of the drawing

The drawing shows a graph of the dependence of rate of PO in time, which can be used to determine the speed of polymerization of PO and duration of induction period in the case of oxyalkylene using DMC complex catalyst.

Description of the preferred embodiments of the invention

Among the oxides of alkylene used in the present invention include ethylene oxide, PO, 1,2 - and 2,3-butylene oxide, in particular PO or PO in a mixture with ethylene oxide. Also suitable higher oxides alkylene, for example WITH5-C20oxides alpha alkylene, the AET butylene oxides. The above-mentioned oxides alkylene can be entered only for the formation of homopolymer products followed by the formation of block-copolymer products or in mixtures for education statistics polyester products or statistical blakelively products.

If the ethylene oxide must be used in combination with another oxide alkylene, it should not be used alone, as there may be formed a variety of foods, which are believed to include a significant number of polyoxyethyleneglycol. Ethylene oxide, however, can be mixed with other oxides alkylene with the formation of statistical products based polyoxyalkylene with terminal hydroxyl groups. If necessary in a simple polyesters with terminal hydroxyl groups blocked by polyoxyethylene, it is preferable to first get the polyol-based, which includes PO or higher oxide alkylene, optionally in a mixture with ethylene oxide to form homopolymer oxide alkylene or statistical copolymer oxide alkylene/ethylene oxide, then add a traditional major or other catalyst to block polyol-basics Oxus these catalysts deactivate DMC catalyst and promotirovat uniform oxoethylidene polyol base.

Polyoxyalkylene obtained according to the present invention may also include residues derived copolymerizate monomers, in addition to 1,2-oxide alkylene, and also considered polyoxyalkylene in the meaning of the term in which it is used in this description. Copolymerizate monomers may, for example, to enter complex essential communication polyoxyalkylene. In a preferred embodiment, residues derived from cyclic ethers, in the most preferred embodiment, 1,2-oxide alkylene include more than 50 molar percent of the recurring polyoxyethyleneglycol components. Examples copolymerizate monomers include various anhydrides of saturated and unsaturated polycarboxylic acids, for example, disclosed in U.S. patent N 5.145.883, and include, but are not limited to, maleic anhydride, 1,2-dimethylmaleic anhydride, succinic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, methylentetrahydrofolate anhydride, incomeinequality anhydride, charentilly anhydride, etc.

Additional copolymerizate monomers include oxetane, 3,3-dimethyloxetane, 3-wine is And N 3.941.849. Among these additional polymerizable monomers include lactones, such as butyrolactone and-caprolacton. Examples of suitable copolymerizate monomers and methods of obtaining simple and polyesters and other polyoxyethyleneglycol can be found in U.S. patents NN 3.278.457; 3.404.109; 5.145.883; 5.358.043; 5.223.583; 4.472.560; 3.941.849; 3.900.518; 3.538.043; 3.404.109; 3.278.458 and 3.278.457, which is incorporated into this description by reference.

In the case of polyoxyethyleneglycol in the lower ranges of equivalent weight, i.e., from 1000 to 2000 daltons, temperature oxyalkylene can be selected in such a way as to be in normal limits, i.e., in the range of 90-110oC. In the case of polyoxyethyleneglycol higher molecular weight, for example, having an equivalent weight of more than 2000-6000 or more daltons, found that normal temperature oxyalkylene often lead to the formation of polyoxyalkylene product having a high polydispersity and high viscosity. In the case of polyoxyethyleneglycol, catalyzed DMC complex catalyst, which is in the mentioned range of high molecular weight, maximum preference is given to carrying out oxyalkylene at temperatures t 125oC to 150oC and most preferably at temperatures in the range 130-150oC.

Not wishing to be bound by any particular theory, I believe that the increased viscosity observed in the case of exceptionally low levels of the DMC complex catalyst in the process of obtaining polyoxyethyleneglycol high molecular weight, due to insufficient diffusion of the oxide (s) of alkylene in the reaction mixture. By raising the reactor temperature to polyoxyalkylene viscosity of the reaction mixture decreases, facilitating increased diffusion of oxide alkylene. Moreover, unexpectedly discovered that high temperature is effective in reducing the induction period, which, otherwise, can be quite long at an exceptionally low levels of DMC catalysts.

An additional way to reduce the induction period is the use of pre-activation masterbatches. In this process, one or more initiators and the required amount of catalyst is added in a suitable reaction vessel such as an autoclave of stainless steel, with the subsequent purge of N2and added to the original colicing number of oxide alkylene to a mixture of activated initiator/oxide alkylene/catalyst, it is preferable to make the appropriate number of masterbatches in another reactor for oxyalkylene, in which, in an advantageous variant, is the additional amount of initiator(s). After that, without any appreciable induction period begins oxyalkylene.

For example, prepares the uterine mixture, which includes 1000 ppm of catalyst is activated, after which 1 wt. percent, representing 10 ppm of catalyst added to the reactor, which is the additional amount of initiator. The temperature of masterbatches in the preferred embodiment, is maintained at a relatively low level, for example at the level of room temperature; uterine mixture is kept in sealed containers to prevent moisture, which can cause deactivation. Reactor for masterbatches may, for example, to connect directly to a reactor for primary oxyalkylene.

Among the initiators suitable for receiving polyoxyethyleneglycol of the present invention include conventional initiating materials having from 1 to 8 or more functional groups, for example, alkanols, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-octanol, 1-decanol, 1-dodecanol, 2-ethylhexanol, onomatology ether of ethylene glycol and so on ; di is ol, diethylene glycol, dipropyleneglycol, 1,4-cyclohexanedimethanol, triethylene glycol and tripropyleneglycol, aliphatic triodes, such as glycerin, trimethylolpropane and trimethylated; tetrahedralization, such as pentaerythritol; pentahydrochloride, such as Alkylglucoside, for example-methylglucoside; hexahydropyridine, for example sorbitol, mannitol, hydroxyethylcellulose and hydroxypropylcellulose; and octahedronical, for example sucrose. Fit can also be different initiators on the basis of starch with a large number of functional groups or oxymetholone species, such as various Novolac and rezol resin obtained by the reaction of formaldehyde and a derivative of phenol, such as phenol or cresol.

With previous DMC complex catalyst, it was found that in the case of the use of the initiators of low molecular weight such as ethylene glycol, propylene glycol, glycerol or trimethylolpropane, duration of induction period is extremely large. Thus, preference is given to using polyoxyalkylene oligomers with hydroxyl functional groups received usual oxyalkylation molecules, having an equivalent weight of preferably from 100 to 500 daltons. Since the equivalent weight of these oligomeric initiators relatively low, the result of oxyalkylene, catalyzed by base, is not a significant level of unsaturation. Oligomeric initiators can be obtained also in the presence of other catalysts.

It has been unexpectedly discovered, however, that when using EA-DMC catalysts for polyoxyethyleneglycol often possible to use initiators lower molecular weight without extremely long induction periods and without deactivation of the catalyst at low levels of the latter. For example, tripropyleneglycol, initiation molecule having an equivalent weight of only 96 daltons, can be used to obtain polyoxyethyleneglycol at levels of catalyst 15 ppm or less, when using catalysts of high activity of the present invention.

In General, the initiator or initiators added to the reactor to polyoxyalkylene, then add the required amount of DMC catalyst. Before adding to the reactor for polyoxyalkylene the mo catalyst is rhenium added amount of the catalyst or it may be suspendibility in a volatile solvent, for example, N-organic, hexane, etc. that can easily be removed from the product when removing unreacted oxide alkylene at the end of the reaction oxyalkylene either removed during the initial blowdown of the reactor. The reactor is typically filled with nitrogen, vacuum, re-filled with nitrogen and re-vacuum to remove air and negligible amounts of moisture that may be present.

After that, the reactor is supplied initial, relatively small, amount destined for the reaction of the oxide alkylene of, typically, less than 10% of the total expected amount of oxide alkylene. Can be added, for example, the number of oxide alkylene sufficient to return the pressure in the reactor to the level of atmospheric. After the initial introduction of the oxide alkylene pressure in the reactor is carefully controlled. The sudden pressure drop in the reactor, caused by the reaction of the oxide alkylene suggests that the catalyst is activated. After this you can enter the additional amount of oxide alkylene, the feed rate depends, in General, the degree of heat removal is possible with this configuration of the reactor. Heat transfer from the reaction mixture obligee is kilena continue to enter into the reactor to obtain a product of the required molecular weight. In the process of filing oxide alkylene its composition may change compared to the baseline on the second, third or fourth composition during oxyalkylene, provided that the composition of the oxide alkylene in the reactor does not change such that essentially includes all of the ethylene oxide, since in this case can be formed polyol comprising homepoliticseconomy components.

EA-DMC complex catalyst for use in the present invention are the polymerization activity equal to or superior to the corresponding figure of providing a reaction rate of about 5 g PO per minute at a concentration of 100 ppm catalyst, measured at 105oC and the pressure PO 10 pounds/inch2(0,703 kg/cm2). The catalyst is conveniently summarized by the polymerization of PO as PO from among oxides of alkylene uses a more just and easily accessible. A level of 100 ppm (the number is determined based on the final weight of the product) is chosen in order to obtain the reaction rate, high enough in the laboratory to provide a simple criterion to the reaction rate, as well as to ensure the levels of catalyst, which is less subject to fluctuations in the measurement is jut because what is the normal temperature at which oxyalkylene. A pressure of 10 pounds/inch2used because it is convenient pressure in the range that is generally considered safe to perform oxyalkylene PO. The reactor used to determine the activity of the catalyst must be autoclave made of stainless steel or other essentially inert metal or with an inert lining, for example, glass, ceramic, Teflon), etc., Autoclave and associated piping, inlet, sealing gasket, mixers, etc. before measuring the activity of the catalyst should be thoroughly cleaned in the usual way.

The catalyst activity is measured by oxopropylidene 70 g polyoxypropylene initiated with glycerol (average molecular weight of 700 daltons) at 105oC with the same amount of catalyst which can provide the content of the catalyst in the polyol as one product of 100 ppm, assuming that the polyol product has a molecular weight of 6000 daltons. A more detailed description of the measurement of the activity of the catalyst are presented in dalea propylene per minute, based on the maximum slope of the curve defining the relationship between the consumed amount of propylene oxide in grams (g PO) and time essentially linear portion of the curve after the induction period, i.e. the maximum tilt or d (g RHO)/dt. An example curve is shown in the drawing, where the activity of the catalyst, which corresponds to the curve, is approximately 28 g PO/min. Minimum activity of the catalyst should be 5 g PO/min, preferably 10 g PO/min or more and preferably 20 g PO/min or more.

The catalysts disclosed in this invention, are in the preferred embodiment, thermostable catalysts. The term "thermostable" refers to a catalyst that retains sufficient catalytic activity at temperatures above 120oC at concentrations of catalyst below approximately 15 ppm relative to the weight of the finished product on the basis of polyoxyalkylene with terminal hydroxyl groups in order before the catalyst is reduced by 50 percent or more compared with the catalytic activity, measured after the induction period could be obtained based product polyoxyalkylene with conradine instantaneous mass of propylene oxide or other oxide alkylene, fed to the reactor at a constant pressure. The temperature at which the catalyst loses its thermal stability is at least 120oC, preferably at least 125oC, more preferably at least 130oC, even more preferably 145oC and most preferably at least 150-160oC.

The number of EA-DMC catalyst used in this invention can range from less than 1 ppm to about 15 ppm, based on the weight polyol as one product, preferably 5-15 ppm and most preferably from about 5 to 10 ppm. At concentrations of 15 ppm or less derived polyol as one product essentially free of transition metal", i.e. contains approximately less than 3.5 ppm Zn and 1.6 ppm, respectively, when the total content of the transition metal of about 5 ppm. The expression "essentially free of transition metal" means that the total number of all transition metal derived from the DMC complex catalyst is approximately less than 8 ppm, preferably about 5 ppm, and most preferably approximately less than 3 ppm.

Double metallocyanide compounds used in the present invention are the product of the preferred embodiment has the General formula M(X)nwhere M is chosen from the group comprising Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II) and Cr(III). In a more preferred embodiment, M is chosen from the group comprising Zn(II), Fe(II), Co(II) and Ni(II). In the above formula X in a preferred embodiment, the anion chosen from the group comprising halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate, n has a value from 1 to 6, which satisfies the valence state of M. examples of acceptable metal salts include, but are not limited to, zinc chloride, zinc bromide, zinc acetate, acetylated zinc, zinc benzoate, zinc nitrate, sulfate, iron (II) bromide, iron (II) chloride cobalt (II), thiocyanate, cobalt (II) formate, Nickel (II) nitrate, Nickel (II), etc. and mixtures thereof.

Water-soluble cyanides of the metals used to obtain double metallocyanide compounds used in the present invention, in the preferred embodiment, have the General formula (Y)aM1(CN)b(A)cwhere M1selected from the group including 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). In a more preferred embodiment, M1choose from a group, the C of these metals. In the above formula Y-ion alkaline or alkaline-earth metal. And anion chosen from the group which includes a halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate, a and b are integers greater than or equal to 1; the sum of charges a, b and C balances the charge1. The number of suitable water-soluble cyanides of metals include, but are not limited to, hexacyanocobaltate potassium (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), hexacyanocobaltate calcium (III), hexacyanoferrate lithium (III), etc.

Examples of dual metallocyanide compounds that can be used in the present invention include, for example, hexacyanocobaltate zinc (III), zinc hexacyanoferrate (III), etc. are further examples of dual metallocyanide compounds listed in U.S. patent N 5.158.922, which is included in the present description by reference.

Among the solid DMC catalyst of the present invention include organic complexing agents. In General, the complexing agents should be relatively water-soluble. To suitable complexing agents are well known in this obla obtain, or immediately after the deposition of the catalyst is preferably dissolved in the same solution(s) that any or both of the metal salts used for the formation of double metallocyanide. Typically use excessive amounts of complexing agents. Preferred complexing agents are water-soluble organic compounds containing heteroatom, which may form a complex with double metallocyanide connection. The number of suitable complexing agents include, but are not limited to, alcohols, aldehydes, ketones, ethers, esters, amides, urea, NITRILES, sulfides and mixtures thereof. Preferred complexing agents are water-soluble aliphatic alcohols selected from the group comprising ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol and tert-butyl alcohol. Most preferred is tert-butyl alcohol (t-butanol). These complexing agents may be indicated by the term "organic complexing agents".

The composition of the solid DMC catalyst of the present invention, in a preferred embodiment, may include from about 5 to 80 wt. % simple powerful groups. The composition of the preferred catalysts is approximately 10-70 wt. % simple polyether polyols; the composition of the preferred catalysts is approximately 15-60 wt. % simple polyether polyols. For a significant increase in catalytic activity compared to catalyst obtained in the absence of simple polyetherpolyols, you need at least about 5 wt. % the latter. The catalysts, which include more than 80 wt. % simple polyetherpolyols, activity usually do not possess. Their selection and use loses a practical sense, because they are usually a sticky paste, not powder solids. Simple polyether polyols suitable for use in obtaining catalysts of the present invention, in the preferred embodiment have at least some tertiary hydroxyl groups. Preferred simple polyether polyols have at least 5 molar percent of the tertiary hydroxyl group; more preferred are polyols having at least about 20 mole % of tertiary hydroxyl groups. Such groups may be introduced through the complete process oxyalkylene oxide, isobutylene the crystals, used catalysts can be obtained in any suitable way. Can be used simple polyether polyols obtained by polymerization with ring opening of cyclic ethers (epoxides, oxetanes, tetrahydrofurane). The polyols can be obtained by any method of catalysis (acid, basic, coordination catalyst). The tertiary hydroxyl group is introduced usually by the inclusion of the monomer of the cyclic ether, which are completely substituted on the atom-carbon cyclic ether. Among the cyclic ethers suitable for the introduction of tertiary hydroxyl groups include, for example, isobutylene oxide, 1,1,2-trimethylethylene oxide, 1,1,2,2-tetramethylethylene oxide, etc., for Example, one simple polyetherpolyols suitable for use in obtaining catalysts of the present invention, receive through education polyoxypropyleneglycol double metallocyanide catalysis followed by the addition of isobutylene oxide to block polyol and convert some or most of the end hydroxyl groups of primary or secondary in tertiary hydroxyl group.

Among the suitable simple politicaly the th-fully carbon substituted Laktionova oxygen. For example, suitable polyol for use in the present invention receive through reaction polyoxypropyleneglycol ,-dimethyl--caprolactone to block polyol and receive the product in which at least some of the terminal hydroxyl groups are tertiary hydroxyl groups.

Preferred simple polyether polyols for preparation of catalysts have, on average, from about 2 to 8 hydroxyl functional groups and an average molecular weight approximately in the range 200-10000, preferably from about 500 to 5000. Most preferred are polyetherdiol and triodes having an average molecular weight of from about 1000 to 4000. Particularly preferred simple polyether polyols are polyoxypropylene and trioli blocked about 1-5 parts of isobutylene oxide. These polyols in the preferred embodiment, are at least about 20% of tertiary hydroxyl groups.

If the catalyst composition is simple polyetherpolyols for double metallocyanide complex catalyst as complexing agents are required as organic complexing agents and prostae the catalyst activity compared with the activity of the same catalyst, obtained without simple polyetherpolyols. However, the required organic complexing agents: catalyst produced in the presence of simple polyetherpolyols, but without organic complexing agents will not contribute to the polymerization of epoxides.

Unexpectedly found that the use of simple polyetherpolyols having a tertiary hydroxyl group, further increased the catalyst activity compared to catalysts made with organic complexing agents and simple polyetherpolyols not having a tertiary hydroxyl groups. These catalysts have extremely high activity towards the polymerization of epoxides and they can be used to produce polyols with very low levels of unsaturation even at relatively high temperatures of polymerization of epoxides.

The method of obtaining EA-DMC catalysts suitable for the present invention includes obtaining a solid DMC catalyst in the presence of organic complexing agents and preferably also in the presence of polyether, which in the preferred embodiment, includes a tertiary hydroxyl group. Water rest the metal under conditions of high shear, i.e., in a homogenizer and/or in the presence of organic complexing agents and simple polyetherpolyols, in the case of the latter. Simple polyetherpolyols in the preferred embodiment is used in a quantity sufficient for the formation of a solid DMC catalyst, which includes approximately 5-80 wt. % simple polyetherpolyols.

In a typical method, aqueous solutions of metal salt (e.g. zinc chloride) and the metal cyanide (e.g., hexacyanocobaltate potassium) initially react in the presence of organic complexing agents (for example, t-butanol) with efficient stirring to form a suspension of catalyst. Mixing in the preferred embodiment, is carried out with high shift parameters using a mixing device such as a homogenizer. Salt of the metal used in excessive quantities. The composition of the suspension of the catalyst is the reaction product of metal salt and metal cyanide, which is double metallocyanide connection. There are, in addition, the salt of the metal (in excess), water and organic complexing agents; each of the components to a certain extent included in the structure of the catalyst.

can be added to the suspension of the catalyst immediately after receipt of the DMC compound. In General, before combining the reagents, it is preferable to mix the complexing agents with any or both of the aqueous solutions. If the complexing agents is instead added to the precipitate of the catalyst, then the reaction mixture should be thoroughly mixed using a homogenizer or mixer with high shear to obtain the most active form of the catalyst. Mixing solutions of metal salt and metal cyanide in the preferred embodiment occurs at a moderately elevated temperature, for example 40-50oC.

Suspension of the catalyst obtained as described previously, can be combined with simple polyetherpolyols, in the preferred embodiment, with the tertiary hydroxyl group. In the preferred embodiment, this is done by mixing with low shear avoid thickening or coagulation of the reaction mixture. After that, the catalyst comprising a polyester, as a rule, separated from the suspension of the catalyst by any suitable means, for example by filtration, centrifugation, merging, etc.

Selected solid catalyst in a preferred embodiment, washed with an aqueous solution, which includes dopolnitelnve aqueous solution of the organic complexing agents with the next stage of the selection of the catalyst. The washing step removes impurities, which, being remote, would deny the catalyst activity. In a preferred embodiment, the amount of organic complexing agents used in the aqueous solution is about 40-70 wt. %. In a preferred embodiment, furthermore, an aqueous solution of the organic complexing agents include a number of simple polyetherpolyols. The number of ordinary polyetherpolyols in aqueous solution in the preferred embodiment, is of the order of 0.5-8 wt. %.

One washing step, however, sufficient catalyst, as a rule, prefer to wash more than once. Subsequent rinsing may be a repetition of the first washing. Subsequent washing in a preferred embodiment, is not water, i.e., it includes only organic complexing agents or a mixture of organic complexing agents and simple polyetherpolyols. After washing, the catalyst will typically prefer to dry under vacuum until until its weight becomes constant.

The preferred products of the method corresponding to the present invention are simple polyether polyols obtained by oxyalkylation with the of epoxy polymers other types can include other monomers, who will copolymerisate with epoxysilane in the presence of the DMC compound. In a way consistent with the present invention, can be obtained from any of the copolymers known in the art, obtained using a conventional DMC catalysts. For example, epoxides copolymerized with oxetane, as described in U.S. patents NN 3.278.457 and 3.404.109, with the formation of polyethers or anhydrides as described in U.S. patents NN 5.145.883 and 3.538.043, with the formation of a complex of the polyester either simple or complex polyether polyols. Obtaining a polyether, a complex of the polyester and simple and complex polyether polyols using double metallocyanide catalysts are fully described, for example, in U.S. patents NN 5.223.583, 5.145.883, 4.472.560, 3.941.849, 3.900.518, 3.538.043, 3.404.109, 3.278.458 and 3.278.457. The above-mentioned U.S. patents relating to the synthesis of polyol using DMC catalysts included in this description in full by reference.

Simple polyether polyols obtained by using the catalysts of the present invention, in the preferred embodiment, have, on average, 2 to 8 hydroxyl functional groups, in the preferred embodiment, is 2-6 and in the most preferred version - 2-3 is more preferred embodiment, approximately 1000-12000 daltons, and in the most preferred embodiment, about 1000-8000 daltons. Equivalent weight can fluctuate within 250-25000 daltons and above, in the preferred embodiment, they are 1000-6000 mm. Dalton.

The following examples are intended only to illustrate the invention. Specialists in this field of technology is obvious the numerous variations within the spirit of the present invention and within the scope defined by the attached claims.

Example 1

Getting solid EA-DMC catalyst, which consists of t-butanol and blocked oxide, isobutylene polyoxypropylene (mol. the weight of 4000 daltons) as the complexing agents

Hexacyanocobaltate potassium (8.0 g) is dissolved in deionized (DI) water (140 ml) in a beaker (Solution 1). Zinc chloride (25 g) dissolved in DI water (40 ml) in a second beaker (Solution 2). In the third glass is Solution 3: a mixture of DI water (200 ml), t-butanol (2 ml), the organic complexing agents and polyol W (8 g). Polyol W produce, getting polyoxypropylene (mol. weight 4000) using a DMC catalyst, followed by blocking its oxide, isobutylene based 1-5 equivalent/hydroxyl group, using the same DMC catalyst.

Solutions 1 and 2 smeshenii t-butanol and DI water (200 ml) and the product is homogenized for 10 minutes.

To the aqueous suspension of hexacyanocobaltate zinc add a Solution of 3 (mixture of polyol/water/g-butanol) and a product with a magnetic stirrer stirred for 2 minutes. To highlight the solids mixture is filtered under pressure through a 5 μm filter.

Filter pressnow cake resuspended in t-butanol (140 ml) and deionized water (60 ml) and the mixture is homogenized for 10 minutes, Add a solution of DI water (200 ml) and the extra amount of polyol W (2 g); the mixture with a magnetic stirrer stirred for 2 minutes and filtered as previously described.

Filter pressnow cake resuspended in t-butanol (200 ml) and homogenized for 10 minutes. Add polyol W (1 g), the mixture with a magnetic stirrer stirred for 2 minutes and filtered. The obtained solid catalyst was dried under vacuum at 50oC (30 inches Hg) (762 mm RT. Art. ) to constant weight. The yield of dry powdered catalyst is about 10,

Elemental, thermogravimetric and mass spectrometric analyses showed: polyol= 18.0 wt. %; t-butanol= 9,0 wt. %; cobalt= 9.5 wt. %; zinc= 20,1 wt. %.

A similar procedure is used for more catalysts, including (75 g) in t-butanol (50 ml) and distilled water (275 ml). Solution 2 get, dissolving hexacyanocobaltate potassium (7.5 g) in distilled water (100 ml). A solution of 3 get mixing t-butanol (2 ml) and distilled water (200 ml).

Solution 2 is added to Solution 1 over 30 minutes with homogenization. Mixing by homogenization additionally continues for 10 minutes. Enter a device for mixing. Add a Solution of 3, and the mixture slowly with a magnetic stirrer stirred for 3 minutes. The mixture is filtered under a pressure of 40 pounds/inch2(2,812 kg/cm2). Filter pressnow cake resuspended in t-butanol (130 ml) and distilled water (55 ml) and the mixture is homogenized for 10 minutes. The mixture is filtered, as described previously. Filter pressnow cake resuspended in pure t-butanol (185 ml) and homogenized for 10 minutes. The mixture is filtered, the cake is dried under vacuum at 60oC. Output: 8,6, the Catalyst used for polymerization of propylene oxide as described in example 7. The rate of polymerization at 105oC, 10 pounds/inch2and 100 ppm of catalyst is 26.3 g PO/minute.

Example 3

Obtaining catalysts on the basis of hexacyanocobaltate zinc by homogenization using t-BU is necobelac potassium (8.0 g) is dissolved in deionized (DI) water (140 ml) in a beaker (Solution 1). Zinc chloride (25 g) dissolved in DI water (40 ml) in a second beaker (Solution 2). In the third glass is Solution 3: a mixture of DI water (200 ml), t-butanol (2 ml) and polyol (2 g polyoxypropylene (mol. weight 4000) obtained by means of DMC catalysts).

Solutions 1 and 2 are mixed using a homogenizer. Immediately to the mixture of hexacyanocobaltate zinc add the mixture (50/50 volume ratio of t-butanol and DI water (200 ml) and the product is homogenized for 10 minutes.

To the aqueous suspension of hexacyanocobaltate zinc add a Solution of 3 (mixture of polyol/water/t-butanol), and the product with a magnetic stirrer stirred for 3 minutes. To highlight the solids mixture is filtered under pressure through a 5 μm filter.

Solid filter pressnow cake resuspended in t-butanol (140 ml) and deionized water (60 ml) and additional polyoxypropylene (mol. weight 4000) (2.0 g); the mixture is homogenized for 10 min and filtered as previously described.

Solid filter pressnow cake resuspended in t-butanol (200 ml) and additional polyoxypropylene (mol. weight 4000) (1.0 g), homogenized for 10 minutes and filtered. The obtained solid capannolo catalyst is 10.7 g

Elemental, thermogravimetric and mass spectrometric analyses showed: polyol= 21,5 wt. %; t-butanol= 7.0 wt. %; cobalt= 11.5 wt. %.

Example 4

Obtaining catalysts on the basis of hexacyanocobaltate zinc using t-butanol and simple polyetherpolyols as complexing agents

Obtaining a catalyst. In odnogolosy (there are 3,785 l) glass reactor high pressure with the possibility of mixing the contents pour the solution hexacyanocobaltate potassium (40 g) in deionized water (700 ml) (Solution 1). Zinc chloride (9125 g) is dissolved in a beaker with deionized water (200 ml) (Solution 2). t-butanol (500 ml) is diluted with deionized water (500 ml) in a beaker (Solution 3). The fourth mixture (Solution 4) receive, suspending polyoxypropylene (mol. weight 4000) (60 g, as in Example 3) in deionized water (1000 ml) and t-butanol (10 ml).

Solutions 1 and 2 combine with stirring (300 rpm). Immediately thereafter, to the resulting mixture hexacyanocobaltate zinc is added slowly a Solution of 3. The mixing speed was increased to 900 rpm and the mixture is stirred for 2 hours at room temperature. The mixing speed is reduced to 300 is the iMER 1, for separation of the solid catalyst.

Solids resuspended in t-butanol (700 ml) and deionized water (300 ml) and stirred at 900 rpm for 2 hours. The mixing speed is reduced to 300 rpm and add 60 g of polyoxypropylene (mol. mass 4000). The mixture is stirred for 5 minutes and filtered as previously described.

Solids resuspended in t-butanol (1000 ml) and stirred at 900 rpm for 2 hours. The mixing speed is reduced to 300 rpm and add 30 g polyoxypropylene (mol. mass 4000). The mixture is stirred for 5 minutes and filtered as previously described. The obtained solid catalyst was dried under vacuum at 50oC (30 inches Hg) to constant weight. The catalyst was easily ground to a fine dry powder.

Elemental, thermogravimetric and mass spectrometric analyses showed: polyol= 45,8 wt. %; t-butanol= 7.4 wt. %; cobalt= 6.9 wt. %.

Example 5

Obtaining a catalyst. Repeat the procedure of Example 4, except that instead of polyoxypropylene mol. mass 4000 use polyoxypropylene mol. weight of 2000, which also receive using DMC catalysis.

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Example 6

Solution 1 get, dissolving hexacyanocobaltate potassium (7.5 g) in distilled water (300 ml) and t-butanol (50 ml). Solution 2 get by dissolving zinc chloride (75 g) in distilled water (75 ml). Solution 3 obtained from t-butanol (2 ml) and distilled water (200 ml).

Solution 2 is added to Solution 1 over 30 minutes with homogenization. Mixing by homogenization additionally continues for 10 minutes. The operation is performed using the device for mixing. Add a Solution of 3, and the mixture slowly with a magnetic stirrer, stirred for 3 minutes. The mixture is filtered under a pressure of 40 pounds/inch2(2,812 kg/cm2). The catalyst is separated, washed and dried as described in Example 2. The catalyst used for polymerization of propylene oxide as described in Example 7. The rate of polymerization at 105oC, 10 pounds/inch2and 100 ppm of catalyst 15.6 g PO/min.

Comparative example 1

Obtaining catalysts of low activity on the basis of hexacyanocobaltate zinc

Hexacyanocobaltate potassium (8,0) is added to deionized water (150 ml) in a beaker and the mixture using a homogenizer mix to Restormel). An aqueous solution of zinc chloride using a homogenizer thoroughly mixed with a solution of cobalt salts. Immediately after combining the solutions to the suspension hexacyanocobaltate zinc is added slowly a mixture of t-butanol (100 ml) and deionized water (100 ml). The mixture is homogenized for 10 minutes.

Solids separated by centrifugation, and then homogenized for 10 minutes with 250 ml of a mixture (70/30 volume ratio) t-butanol and deionized water. The solids are again separated by centrifugation, and then homogenized for 10 minutes with 250 ml of t-butanol. The catalyst was separated by centrifugation and dried in a vacuum oven at 50oC and 30 inches Hg to a constant weight. The catalyst activity is 3.84 g PO/min.

Example 7

Polymerization of epoxy compounds: experiments to determine the rate at which is the Common procedure

In one litre reactor with stirring contribute Polyoxypropylenediamine (mol. weight 700) starter (70 g) and DMC complex catalyst (0,057 g; 100 ppm in the final polyol). The mixture is stirred, heated to 105oC and under vacuum of trilogo starter remove minor amounts of water. The reactor vacuumized around the additional amount of propylene oxide is administered only after a rapid pressure drop in the reactor; the pressure drop indicates the activation of the catalyst. After checking the activation of the catalyst is gradually introduced the rest of propylene oxide (490 g) while maintaining the pressure in the reactor at the rate of 10 pounds/inch2. After complete addition of propylene oxide the temperature of the mixture is maintained at level 105oC to establish a constant pressure. After the polyol as one product under vacuum to remove residual amounts of unreacted monomer, polyol is cooled and recovered.

To determine the reaction rate, draw the curve of dependence of rate of PO (g) the duration of the reaction (min) (see drawing). To determine the reaction rate in grams conversion of PO per minute measure the slope at the steepest point. The intersection of this line and the horizontal line, which is a continuation of the baseline curve is taken as the induction time (in minutes) required for the catalyst acquired activity. The results of measurements of the reaction rate are summarized in Table 1.

When using this technique to measure the rate of polymerization PO catalysts used in the method corresponding to the present isolator and 105oC (see drawing) or higher. The rate of polymerization of epoxy compounds with catalysts, which include simple polyetherpolyols having a tertiary hydroxyl group is also significantly higher than in the case of the use of such catalysts obtained in the simple presence of polyether polyols with terminal hydroxyl groups, but without tertiary hydroxyl groups.

Example 8

Synthesis of simple polyetherpolyols: polyoxypropylene (mol. weight 8000) (8K-D)

In one litre reactor with stirring contribute Polyoxypropylenediamine (mol. weight of 1000) starter (77 g) and the catalyst on the basis of hexacyanocobaltate zinc, including 23% 4K diol blocked by isobutylene oxide, as in Example 1 (0,009 g, 10 ppm). The mixture is stirred, heated to 105oC for 0.5 hour was stripped under vacuum to remove from delovogo starter insignificant quantities of water. After removal of the temperature of the reaction mixture increased to 145oC. In the reactor, vakuumirovaniya approximately 30 inches Hg, serves PO (12 g), the pressure in the reactor is carefully controlled. Additional propylene oxide is administered only after a rapid pressure drop in the reactor; drop giving the Xia remainder PO (512 g) for approximately 4 hours. When you are finished adding PO the temperature of the mixture is maintained at level 145oC to establish a constant pressure. After the polyol as one product under vacuum at a temperature of 60oC remove residual amounts of unreacted monomer. Unsaturation polyol as one product is 0,007 IEC unsaturation per gram polyol, the polydispersity is 1.15.

Comparative Example 4

In the same reactor as in Example 8, enter Polyoxypropylenediamine (mol. weight 725) starter (65 g) and a complex catalyst based hexacyanocobaltate zinc digimon as complexing agents (Comparative Example 2; 0,0166 g, 25 ppm) to obtain polyoxypropylene (mol. mass 8000). The mixture is stirred, heated to 105oC for 0.5 hour was stripped under vacuum to remove from delovogo starter insignificant quantities of water. After removal of the temperature of the reaction mixture is raised to 130oC. In the reactor, originally vakuumirovaniya approximately 30 inches Hg, serves PO (11 g), the pressure in the reactor is carefully controlled. After checking the activation of the catalyst as described in Example 8, PO added at a rate of 2.4 g/minute. When the added amount of PO is giving PO stops due to high pressure in the reactor. The temperature of the mixture is maintained at level 130oC to establish a constant pressure. After the polyol as one product under vacuum at a temperature of 80oC remove residual amounts of unreacted monomer. Polyol as one product has a molecular weight of about 4,400 daltons, unsaturation 0,031 IEC/g and a polydispersity of 1.46. The composition of the polyol as one product is 3.9 and 10 ppm Co and Zn, respectively.

Comparative Example 4 shows that the pre-catalysts of low activity, even at a much higher level of 25 ppm, are unsuitable for obtaining polyoxyethyleneglycol high molecular weight with low levels of unsaturation and low polydispersity at low levels of catalyst. Previous catalyst deaktivirovana after reaching a molecular weight of only 4400 daltons. Even when this molecular weight, the polydispersity was very high (1,46) and the level of unsaturation was also very high, approaching the limits formerly provided the usual basic catalysis. Residual levels of catalyst without the use of methods for removing the residual catalyst was superior to the determined speedplays by the claims.

1. The method of obtaining substantially free of transition metals polyether-based polyoxyalkylene with terminal hydroxyl functional groups by oxyalkylene containing one or more substituted hydrogen atoms oxyalkylene initiation of a molecule or molecules of one or more oxide alkylene and polymerization in the presence of double metallocyanide complex catalyst oxyalkylene with subsequent regeneration is substantially free of transition metals polyether-based polyoxyalkylene with terminal hydroxyl functional groups, characterized in that the catalyst the polymerization rate of oxide alkylene defined relative to the oxypropylation with propylene oxide, is greater or equal to approximately 5 g of propylene oxide/min at 105oC, at a pressure of propylene oxide to 0.68 bar and content of 100 ppm catalyst, based on weight of polyether-based polyoxypropylene where the concentration mentioned double metallocyanide catalyst in the process mentioned oxyalkylene is not more than about 15 ppm, based on weight is uppada.

2. The method according to p. 1, characterized in that the above simple polyester-based polyoxyalkylene with terminal hydroxyl functional groups is not subjected to processing to remove residual double metallocyanide complex catalyst prior to regeneration.

3. The method according to p. 1 or 2, characterized in that the concentration of the mentioned double metallocyanide complex catalyst in the process mentioned oxyalkylene is not more than 10 ppm.

4. The method according to any of the preceding paragraphs, characterized in that the speed of the oxypropylation mentioned double metallocyanide complex catalyst is at least 10 g of propylene oxide/min.

5. The method according to p. 4, characterized in that the speed of the oxypropylation mentioned double metallocyanide complex catalyst is not less than 20 g of propylene oxide/min.

6. The method according to any of the preceding paragraphs, characterized in that the said one or more oxide alkylene choose from among (a) of propylene oxide, in) oxide, 1,2-butylene,) oxide, 2,3-butylene, d) oxide, isobutylene, mixtures of one or more of the paragraphs (a)- (d); mixtures of one or more of the point characterized in that the said double metallocyanide complex catalyst is a thermostable double metallocyanide complex catalyst.

8. The method according to p. 7, characterized in that the said oxyalkylene carried out at a temperature of more than 120oC.

9. The method according to p. 7, characterized in that the said oxyalkylene carried out at a temperature of more than 135oC.

10. The method according to any of the preceding paragraphs, characterized in that the above simple polyester-based polyoxyalkylene with integral hydroxyalkyl functional groups has an equivalent weight of more than 2000 daltons and a polydispersity of approximately 1.25 or less.

11. The method according to any of the preceding paragraphs, characterized in that it includes, before mentioned oxyalkylene, getting masterbatches pre-activated initiator /double metal catalyst by means of: i) obtaining a mixture of initiating molecules (molecules) and double metallocyanide complex catalyst oxyalkylene; (ii) adding to the above mixture a certain amount of one or more oxide alkylene to establish what itiator/double metallocyanide complex catalyst after restoring the partial pressure of the above-mentioned oxide alkylene and adding at least part of the mentioned pre-activated uterine mixture in the reactor to oxyalkylene.

12. The method according to p. 11, characterized in that the said mixture of the initiator/catalyst/oxide alkylene heated to a temperature above 125oWith up until the pressure drop will indicate the activation of the catalyst and carry out oxyalkylene additional oxide alkylene at a temperature of from about 70oWith up to temperature inactivation of the catalyst.

13. Polyoxyalkylene with terminal hydroxyl functional groups, obtained by the method according to any of paragraphs. 1-12, which has an average equivalent molecular weight in the range from 2000 to 10,000 daltons and a polydispersity Mw/Mnless than 1.25.

14. Polyol under item 13, characterized in that the polydispersity is less than 1.20.

15. Polyoxyalkylene obtained by the method according to p. 1, raw to remove the residual catalyst.

 

Same patents:

The invention relates to polyetherpolyols, the method of its production, to polyetherpolyols mixture containing the polyol, and the hard polyurethane foam and can be used as insulating material for refrigerators, freezers in industrial plants, construction industry

-oximeter-oxy(oxo) -propyl-anhydride-succinic acid (peak)" target="_blank">

The invention relates to the production of PEAK that can be used as hardeners polymer compositions, varnishes, waxes, thickeners, reagents for the synthesis of surfactants, ion exchange polymers, flocculants water, floating agents, etc

The invention relates to methods for polyoxyethyleneglycol (co)polymerization of cyclic ethers and polyols in the presence of a catalyst based on heteropolyacids (CCP), in particular, the (co)polymerization of tetrahydrofuran, 1,2-alkalisation, epichlohydrin and polyols

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

The invention relates to the production of polyoxyethyleneglycol, in particular to a method for polytetrahydrofuran or complex monoamino monocarboxylic acids with 1 to 10 carbon atoms

FIELD: polymer production.

SUBSTANCE: polyoxyalkylene-polyols are obtained via direct polyoxyalkylenation of acid-sensitive low-molecular initiator with molecular weight below 400 Da in presence of double complex metal cyanide catalyst. Process comprises: (i) creation of appropriate conditions in reactor of polyoxyalkylenation in presence of double complex metal cyanide catalyst; (ii) continuously feeding into reactor alkylene oxide and above-mentioned initiator; and (iii) discharging polyether product. Loss of catalyst activity is reduced by performing at least one of the following operations: acidification of acid-sensitive low-molecular initiator before feeding it into reactor; and treatment of the same with effective amount of a substance other than acid, which reacts with base or absorbs base, before feeding it into reactor.

EFFECT: prevented catalyst from loosing its activity and essentially decreased high-molecular fraction and polydispersity of polyoxyalkylene-polyols.

21 cl, 2 dwg, 2 tbl, 3 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention provides double metal cyanide catalysts for production of polyetherpolyols via polyaddition of alkylene oxides to starting compounds containing active hydrogen atoms, which catalysts contain double metal cyanide compounds, organic complex ligands, and α,β-unsaturated carboxylic acid esters other than above-mentioned ligands.

EFFECT: considerably increased catalytic activity.

6 cl, 16 ex

FIELD: organic chemistry, polymer materials.

SUBSTANCE: polyester-polyols are obtained by double metalcyanide catalyzed polyaddition of alkylenoxide to starting material containing active hydrogen atoms. Alkylenoxide is continuously fed into reactor during induction period while maintaining constant pressure in reactor.

EFFECT: method for polyester-polyol production with decreased induction time.

2 ex, 1 dwg

FIELD: polymerization catalysts.

SUBSTANCE: catalyst is composed of double metal cyanide compound, organic ligand, and two complexing components other than precedent organic ligand and selected from group including: polyethers and polyesters, glycidyl ethers, esters from carboxylic acids and polyatomic alcohols, bile acids, bile acid salts, bile acid esters, bile acid amides, and phosphorus compounds, provided that selected complexing components belong to different classes.

EFFECT: substantially increased catalytic activity.

5 cl, 1 tbl, 16 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to improved method of preparing double metal cyanide catalysts for synthesis of polyether-polyols via polyaddition alkylene oxides to starting compounds possessing active hydrogen atoms. Method comprises following steps: (i) mixing one or several solutions of water-soluble salts of Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(VI), Cu(II), or Cr(III) with solution of water-soluble cyanide ions-containing salt or acid 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), or V(V) with the aid of mixing nozzle, preferably jet disperser; (ii) isolation of catalyst from resulting dispersion; (iii) washing; and (iv) drying.

EFFECT: increased catalytic activity, reduced particle size, and narrowed size distribution of particles in polyether-polyols production process.

8 cl, 5 dwg, 9 ex

FIELD: continuous production of polyoxyalkylene polyether product.

SUBSTANCE: proposed method includes introduction of first portion of mixture of double metallocyanide catalyst with initial starter into continuous-action reactor for initiating polyoxyalkynylation of initial starter after introduction of alkylene oxide. Proposed method includes: (a) continuous introduction of one or more alkylene oxides into said reactor; (a')continuous introduction of mixture of double metallocyanide catalyst with starter into inlet hole of said reactor for maintenance of catalytic activity at required level; (a")continuous introduction of one or several additional starters in addition to starter introduced into said inlet hole of reactor together with catalyst; these additional starters may be identical to said starter or may differ from it and may contain additional double metallocyanide catalyst; (b) polyoxyalkynylation of combined starters of continuous action of stages (a), (a') and (a") for obtaining polyoxyalkylene polyether product having required average molecular mass; and (c) continuous removal of said polyoxyalkylene polyether product from reactor. Proposed method makes it possible to obtain polyoxyalkylene polyether product of low degree of nonsaturation and narrow polydispersity practically containing no fractions of high molecular mass.

EFFECT: enhanced efficiency.

29 cl, 6 dwg, 7 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to improved method for preparing double metal cyanide catalysts effective to catalyze synthesis of polyetherpolyols via polyaddition of alkylene oxides to starting compounds containing active hydrogen atoms. Method is characterized by that aqueous solutions of metal salt and metal cyanide salt are first brought to react in presence of organic complex ligands and, if necessary, one or several other complexing components to form dispersion of double metal cyanide catalyst, which is filtered to give filtration precipitates. The latter are washed with one or several aqueous or nonaqueous solution of organic complex ligands in flowing washing mode and, if necessary, one or several other complexing components, after which washed filtration precipitates are dried after optional squeezing and mechanical removal of moisture. Washing and drying stages are performed on the same filter.

EFFECT: significantly simplified process due to avoided repetitive redispersing of catalyst followed by transferring filtration precipitate to another equipment.

9 cl, 13 ex

FIELD: chemistry.

SUBSTANCE: in phosphazene, applied on carrier, catalyst for cyclic monomer polymerisation or for substituent substitution in compound or for carrying out reaction with formation of carbon-carbon bond, carrier is insoluble in used solvent and has group, which is able to form bond with group described with general formula (1) where n is integer in interval from 1 to 8 and represents number of phosphazene cations, Zn- is anion of compound, containing atoms of active hydrogen in form obtained as result of release of n protons from compound, which contains atoms of active hydrogen, in which there are , at most, 8 atoms of active hydrogen; each of a, b, c and d represents positive integer equal 3 or less; R represents similar or different hydrocarbon groups, containing from 1 to 10 carbon atoms, and two R, located on each common nitrogen atom, can be bound with each other with formation of ring structure; R1 represents hydrogen atom or hydrocarbon group, containing from 1 to 10 carbon atoms; D represents direct bond or divalent group able to bind N with carrier. Described are phosphazene compound and phosphazene salts and methods of cyclic monomer polymerisation, substitution of substituent in compound and carrying out of reaction with formation of carbon-carbon bond using applied on carrier catalyst. According to invention method polymerisation of cyclic monomers, substitution of substituents, reactions with formation of carbon-carbon bond, etc. can be carried out with extremely high efficiency.

EFFECT: increase of efficiency of carrying out different organic reactions and absence of activity decrease even after removal and re-use of catalyst, economic benefit.

10 cl

FIELD: chemistry.

SUBSTANCE: proposed method involves interaction of, (i) at least one water soluble metallic salt, (ii) at least one water soluble metal-cyanide salt, (iii) at least one organic complexing ligand, (iv) at least one water soluble alkaline metallic salt and, not necessarily, (v) at least one functionalised polymer in conditions of precipitation, enough for the formation of a catalyst and addition of at least one water soluble alkaline metallic salt in an amount which will ensure its amount in the specified catalyst is roughly from 0.4 to 6% of the total mass of the double meta-cyanide catalyst. Also declared is the double metal-cyanide catalyst obtained using the specified method.

EFFECT: acceptable catalyst activity and the possibility of using it for obtaining polyols with the reduction in the levels of high-molecular tail fractions.

14 cl, 16 ex, 7 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns mix with activated initiation agent, which can be applied in obtaining polyalkylenepolyenes. Claimed mix with activated initiation agent includes (a) at least one initiation agent activated in advance and comprised by: (i) at least one of first initiation agents with equivalent mass of at least 70; (ii) at least one epoxide; and (iii) at least one DMC-catalyst; and (b) at least 2 mol % per quantity of initiation agent(s) activated in advance of one of second initiation agents with equivalent mass less than equivalent mass of first initiation agent.

EFFECT: elimination of necessity to synthesise expensive initiation agents with high molecular mass with catalysis facilitated by potassium hydroxide in separate assigned reactor.

7 cl, 2 ex

FIELD: polymer production.

SUBSTANCE: polyoxyalkylene-polyols are obtained via direct polyoxyalkylenation of acid-sensitive low-molecular initiator with molecular weight below 400 Da in presence of double complex metal cyanide catalyst. Process comprises: (i) creation of appropriate conditions in reactor of polyoxyalkylenation in presence of double complex metal cyanide catalyst; (ii) continuously feeding into reactor alkylene oxide and above-mentioned initiator; and (iii) discharging polyether product. Loss of catalyst activity is reduced by performing at least one of the following operations: acidification of acid-sensitive low-molecular initiator before feeding it into reactor; and treatment of the same with effective amount of a substance other than acid, which reacts with base or absorbs base, before feeding it into reactor.

EFFECT: prevented catalyst from loosing its activity and essentially decreased high-molecular fraction and polydispersity of polyoxyalkylene-polyols.

21 cl, 2 dwg, 2 tbl, 3 ex

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