Double metallocyanide catalysts containing polymers functionalityand

 

(57) Abstract:

The invention relates to a double metallocyanide catalysts suitable for the polymerization of epoxy compounds. The catalyst according to x-ray powder diffraction is not crystalline. It contains: a) double metallocyanide connection; b) organic complexing agent and (C) from 2 to 80 wt.% functionalized polymer or water-soluble salt. The catalysts according to the invention is easy to get and to select, they are, in essence, are non-crystalline and have a high activity for polymerization of epoxy compounds. The polyols obtained by using the catalyst according to the invention have a low degree of unsaturation, low viscosity and low content of tail fraction of high molecular weight. 3 C.p. f-crystals, 1 tab., 3 Il.

The technical field to which the invention relates

The invention relates to a double metallocyanide (DMC) catalysts suitable for the polymerization of epoxy compounds. In particular, the present invention relates to the DMC catalysts which have high activity, are not essentially crystalline and contain functionalized floor is ti, used in the production of polyurethanes.

Background of the invention

Double metallocyanide complexes are well known as catalysts for the polymerization of epoxy compounds. Mentioned active catalysts allow to obtain the polyether polyols having a low degree of unsaturation compared with similar polyols obtained by using the basic (KOH) catalysis. The above catalysts can be used to produce a variety of polymer products, including polyethers, polyesters and simple and complex polyether polyols. The above-mentioned polyols can be used to obtain a polyurethane coating materials, elastomers, sealants, foams and adhesives.

DMC catalysts receive, usually by reaction of aqueous solutions of salts of metals and cyanides of metals with the formation of DMC compound. In the process of obtaining the above-mentioned catalysts include organic complexing agent is a low molecular weight, usually a simple ether or alcohol. Obtaining a typical DMC catalysts is described, for example, in U.S. patents 3427256, 3829505 and 5158922.

For several decades for pollinose. The most common catalyst include organic complexing agent (usually glyme), water, salt of the metal with a slight excess (usually zinc chloride) and DMC compound. The activity of polymerization of epoxy compounds, surpassing the activity, provide commercial standard (KOH) catalyst, was considered sufficient. Later began to understand that successful commercialization polyols obtained using DMC catalysts, the value could be more active catalysts.

The author of the present invention have been recently described, essentially amorphous DMC catalysts with exceptionally high activity towards the polymerization of epoxy compounds (see U.S. patent 5470813). Mentioned by the author were also described is highly active DMC catalysts, which, along with the organic complexing agent is a low molecular weight, is approximately 5 to approximately 80% (wt. simple polyester, for example, polyoxypropyleneglycol (see U.S. patent 5482908 and 5545601). Compared to the previously used DMC catalysts mentioned DMC catalysts described in U.S. patent 5470813, 5482908 and 5545601 have Velikiye catalysts have a high activity level, that allows their use in very low concentrations, which are often low enough to eliminate any need for removal of the above-mentioned catalyst from the polyol.

The most active of the currently known DMC catalysts are, in General, a relatively low degree of crystallinity. The result of the homogenization of the reacting substances to facilitate the effective inclusion of organic complexing agent in the structure of the catalyst or include polyether (usually, polyetherpolyols) in the catalyst composition is getting DMC catalysts having a high activity level. Data of powder x-ray diffraction analysis indicate that the catalysts mentioned type, essentially devoid of crystallinity (see Figure 1).

Even the best known DMC catalysts could be improved. For example, the catalyst U.S. patent 5470813 prone to the formation of polyols with a high content of tail polianovich fractions of high molecular weight and/or gelation in the case of obtaining the polyol in "stressful" conditions (for example, when the fast track add epoxysilane, very low cone high molecular weight may also contribute to the acquisition of the polyols with unacceptably high viscosity and may hinder the processing of polyurethane foams.

The process of obtaining catalysts can be improved. Most of the DMC catalysts known in the art, are fine particles, clogging filters, so for separation of catalyst have to resort to centrifugation (see, for example, U.S. patent 5470813). In a preferred embodiment, the above-mentioned catalyst can be easily washed and allocate by simple filtration. In addition, the majority of DMC catalysts before use dried to a solid pellet and the pellet is necessary to grind with the application of a considerable effort to obtain engineering powder (see, for example, a patent application in Japan 3-245848). The need to make the DMC catalysts in powder requires considerable time and effort.

In General, the necessary new DMC catalysts. In a preferred embodiment, the above-mentioned catalysts must be essentially non-crystalline and highly active. In a preferred embodiment, the above-mentioned catalysts should be easy to stand out in the process of getting through simple filtration and dried to a pellet which is easily transformed into powder. An ideal catalyst would provide iloveu tail fractions of high molecular weight and to reduce the number of problems associated with gel formation and contamination of the reactor. The ideal catalyst should be sufficiently active for use in very low concentrations, in a preferred embodiment, at concentrations low enough to eliminate any need for removal of the above-mentioned catalyst from the polyol.

Summary of the invention

The present invention is a double metallocyanide (DMC) catalyst suitable for the polymerization of epoxy compounds. The composition of the above-mentioned catalyst is DMC compound, an organic complexing agent, and about 2 to about 80% (wt.) functionalized polymer or water-soluble salt obtained from the above-mentioned polymer. The present invention also includes a method of obtaining the above-mentioned catalysts and the method of obtaining polyepoxide connection with the above-mentioned catalysts.

The author of the present invention surprisingly found that DMC catalysts, which include functionalized polymer corresponding to the definition below, are essentially non-crystalline and, in addition, have a high activity is provided DMC catalysts, containing polyethers (see U.S. patent 5482908 and 5545601) and, in General, exceeds activity comparable catalysts obtained in the absence of the above functionalized polymer.

The catalysts corresponding to the present invention, it is easy to stand out in the cooking process by simple filtration, and, thus, eliminate the need for centrifugation. Along with this, the dried catalysts corresponding to the present invention, are easily converted into engineering powders without the need for grinding or milling with application of a considerable effort.

Polymerization of epoxy compounds using catalysts of the present invention provides for obtaining polyols having a very low degree of unsaturation. In addition, the polyols obtained from the catalysts of the present invention include small amounts paleologou tail fractions of high molecular weight and reduce the number of problems associated with gel formation and contamination of the reactor, even in the case where the above-mentioned polyol get in "stressful" conditions.

It is quite obvious that the key point poesy forms mentioned catalysts. A consequence of the inclusion in the composition of the above-mentioned catalyst functionalized polymer is getting, essentially non-crystalline catalyst, which is easily obtained and released, which has a high activity and ensures polyether polyols and high quality.

Brief description of figures

The Figure 1 presents the x-ray powder diffraction pattern of the catalyst corresponding to the present invention (Example 4), the DMC catalyst containing a simple polyester obtained according to the U.S. patent 54829088 (see Comparative Example 9) and, in fact, amorphous catalyst obtained in the absence of additives functionalized polymer, as described in U.S. patent 5470813 (see Comparative Examples 10 and 11). The Figure 2 presents the traditional hexacyanocobaltate-glenavy catalyst. The Figure 3 shows hexacyanocobaltate zinc obtained without complexing agent.

Detailed description of the invention

The catalysts corresponding to the present invention, include dual metallocyanide (DMC) compound, an organic complexing agent, and about 2 to about 80% (wt.) functionalized floor is Lithuania in the present invention, are the reaction products of water-soluble metal salt and water-soluble metal cyanide. Water-soluble salt of the metal, in the preferred embodiment, has the General formula M(X)nwhere M is chosen from the group composed 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(IV), W(VI), Cu(II) and Cr(III). In a more preferred embodiment, M is chosen from the group composed of Zn(II), Fe(II), Co(II) and Ni(II). In the above formula X, in the preferred embodiment, is an anion selected from the group which includes a halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate; n has a value from 1 to 3, which satisfies the valence state of M. examples of suitable metal salts include, but not limited to, zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetone, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, cobalt (II) chloride, cobalt (II) thiocyanate, Nickel (II) formate, Nickel (II) nitrate, etc., and mixtures thereof.

Water-soluble cyanides of the metals used to obtain double metallocyanide compounds used in the present invention, suppose the ora consists 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). In a more preferred embodiment, M' is chosen from the group composed of Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II). In one of the above-mentioned water-soluble metal cyanide may include one or more of these metals. In the above formula Y - ion of an alkali metal or alkali earth metal ion; And a is an ion selected from the group which consists of halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate. As a and b are integers greater than or equal to 1; the sum of charges a, b and C balances the charge of M'. Suitable water-soluble metal cyanide include, but not limited to, potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III), lithium hexacyanoferrate (III), etc.

Examples of dual metallocyanide compounds which can be used in the present invention include, for example, zinc hexacyanocobaltate (III), zinc hexacyanoferrate (III), zinc hexacyanoferrate (II), Nickel (II) hexacyanoferrate (II), cobalt (II) hexacyanocobaltate (II22, description of which is included in the present description by reference.

The composition of the DMC catalysts of the present invention includes an organic complexing agent. Complexing agent, in General, should be relatively soluble in water. The number of suitable complexing agents include complexing agents, well known in the art, for example, described in U.S. patent 5158922. Mentioned complexing agent is added either in the process of receiving, either directly after deposition of the above-mentioned catalyst. As a rule, use excessive amounts of complexing agent. 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 not limited to, alcohols, aldehydes, ketones, ethers, esters, amides, urea, NITRILES, sulfides and mixtures thereof. Among the preferred complexing agents are water-soluble aliphatic alcohols, which are selected from the group botilony alcohol. Particular preference is given to tert-butyl alcohol.

A key component referred to DMC catalysts of the present invention is a functionalized polymer or water-soluble salt. By "functionalized polymer" means a polymer, except polyether, which includes one or several functional groups including oxygen, nitrogen, sulfur, phosphorus or halogen, with the above-mentioned polymer or water-soluble salt have a relatively high solubility in water, i.e., at least about 3% (wt.) the above-mentioned polymer or its salt are dissolved at room temperature in water or a mixture of water with an organic solvent miscible with water. Examples of organic solvents, miscible with water, are tetrahydrofuran, acetone, acetonitrile, t-butyl alcohol, etc., the solubility is important to include the aforementioned functionalized polymer in the structure of the above-mentioned catalyst in the process of formation and deposition mentioned double metallocyanide connection.

Preferred functionalityand polymers have the General structure

< / BR>
where R' is hydrogen, -Aoluguya-HE, -NH2, -OTHER, -NR2, -SH, -SR, -COR, -CN, -Cl, -Br, -C6H4-IT, -WITH THE6H4- (CH3)2HE, -CONH2, -CONHR, -CO-NR2, -OR, -NR2, -NHCOR, -NRCOR, -COOH, -COOR, -CHO, -OCOR, -COO-R-OH, -SO3H, -CONH-R-SO3H, pyridinyl and pyrrolidinyl, where R is a C1-C5alkyl or Allenova group, n has a value in the range of about 5 to about 5000. In a more preferred embodiment, n has a value between approximately 10 to approximately 500.

Optional, the said polymer includes a repeating structural unit derived from defunctionalizing vinyl monomer, for example, olefin or diene, for example, ethylene, propylene, butylene, butadiene, isoprene, styrene, etc., provided that the said polymer or its salt have relatively good solubility in water or mixtures of water and organic solvent miscible with water.

The number of suitable functionalized polymers include, for example, poly(acrylamide), a copolymer of polyacrylamide and acrylic acid, poly(acrylic acid), poly(2-acrylamide-2-methyl-1-propanesulfonic acid), copolymer of acrylic and maleic acid, poly(Acrylonitrile), poly(alkylacrylate alcohol), poly(N-vinyl pyrrolidone), copolymers of poly(NN-vinylpyrrolidone and acrylic acid, poly(N, N-dimethylacrylamide), poly(vinylethylene), poly(4-vinylphenol), poly(4-vinylpyridine), poly(vinyl chloride), copolymer of polyacrylic acid and styrene, poly(vinylsulfonate), sodium salt of poly(vinylsulfonate), etc.

In other preferred catalysts of the present invention, the aforementioned functionalized polymer selected from the group comprising polyesters, polycarbonates, polymers oxazoline, polyalkylimide, copolymers of maleic acid and maleic anhydride, hydroxyethyl cellulose, starches and Polyacetals. Consequently, the said functionalized polymer can be, for example, poly(etilenglikolevye), poly(dipropyleneglycol), poly(1,6-hexaniacinate), poly(2-ethyl-2-oxazoline), copolymer has polyvinylbutyral, vinyl alcohol and vinyl acetate, etc. and their salts.

In the catalyst composition of the present invention is approximately from 2% (wt.) up to about 80% (wt.) (in terms of the total number of catalyst) functionalized polymer. In a preferred embodiment, the composition of the above-mentioned catalysts which may range, approximately, 10% (wt.) up to about 60% (wt.). You can significantly improve the activity of the catalyst is necessary, at least about 2% (wt.) the above-mentioned polymer, compared with the catalyst, obtained in the absence of the above-mentioned polymer. The catalysts, which include approximately more than 80% (wt.) the above-mentioned polymer, are not, in General, more active, and their selection is often difficult.

The molecular weight of the functionalized polymer may vary within a very wide range. In a preferred embodiment, srednekislye molecular weight is in the range of about 300 to about 500000; a more preferred range is about 500 to about 50000.

The author of the present invention surprisingly found that DM catalysts, which include functionalityand polymers, described earlier, are essentially non-crystalline and, in addition, have a high activity towards the polymerization of epoxy compounds. The phrase "essentially non-crystalline" refers to catalysts that do not have clearly defined crystalline structure or feature is anouska powder diffraction pattern of traditional catalysts, including hexacyanocobaltate zinc and glyme (for example, catalysts described in U.S. patent 5158922), contains many sharp lines, indicating the high crystallinity of the above-mentioned catalysts (see Figure 2). Hexacyanocobaltate zinc obtained in the absence of a complexing agent, also has a high degree of crystallinity (see Figure 3). In contrast, the catalysts corresponding to the present invention, like the catalysts described in U.S. patent 5470813 and 5482908 are essentially no crystalline (see Figure 1 and Comparative Examples 9-11).

The activity of the catalysts of the present invention, comparable to the activity connected to the DMC catalysts, which include polyethers (see U.S. patent 5482908 and 5545601) and, in General, exceeds the activity of comparable catalysts obtained in the absence of a functionalized polymer. As shown in the Table (below), the activity of the catalysts of the present invention, greater than about 15 g RO (propylene oxide)/min at 20-25 ppm (parts per million) of the catalyst and 105oWith, compared to the activity that constitutes less than 10 g RO/min at 20 ppm catalysts U.S. patent 5470813 and 5482908, the catalysts corresponding to the present invention, are not essentially crystalline or amorphous. In fact, the aforementioned x-ray powder diffraction patterns of the catalysts of the present invention, surprisingly reminiscent of the pattern described by the author of the present invention in the previously mentioned patents. Description of the U.S. patent 5470813 and 5482908 relating to the determination of the properties of the catalyst by x-ray powder diffraction, included in the present description by reference.

For catalysts of the present invention is characterized by the almost complete absence of sharp lines and a relatively small number of signals. The Figure 1 presents the x-ray powder diffraction pattern of the catalyst corresponding to the present invention (which, as a functionalized polymer includes poly(vinylethylene ether), see Example 4), the DMC catalyst containing a simple polyester described in U.S. patent 54829088 (see Comparative Example 9) and, in fact, an amorphous catalyst containing no polymer additives, as described in U.S. patent 5470813 (see Comparative Examples 10 and 11). As shown in the figures, the e differences types of polymer additives (easy polyester or functionalized polymer). The exact position of the peaks to some extent depends on the amount of functionalized polymer, the nature of the above-mentioned polymer and the nature of the organic complexing agent. In General, the degree of crystallinity decreases with increasing content of the functionalized polymer.

Preferred catalysts corresponding to the present invention show only a relatively sharp peak in the x-ray powder diffraction pattern with interplanar distance of, approximately, from 3.7 angstroms to about 3.8 angstroms, which corresponds to the angle of about 23 degrees two theta to approximately 24 degrees two theta. At this peak the size of the crystallite is about 280 angstroms, which corresponds to the value premaxillae total width (FWHM) of approximately of 0.3. The remainder of the preferred catalysts, judging by x-ray powder diffraction pattern is essentially non-crystalline; the principal place mentioned on the diffraction pattern take two additional major broader peak centered around the interplanar spacings, comprising, approximately, from 4.7 to 4.9 angstroms (Okano additional much smaller non-crystalline peaks. The Figure 1 shows the preferred catalyst corresponding to the present invention (functionalized polymer=poly(vinylethylene ether), see Example 4), which has peaks of x-ray powder diffraction pattern with interplanar distance (angstroms): 3,75, 4,81 and 6.06.

The catalysts corresponding to the present invention, are easily distinguished in the process of getting through a simple filter that eliminates the need for centrifugation. As shown in the following examples, when washing and the allocation of the above-mentioned catalyst may be used simple filtration under pressure. As shown in Comparative Examples 10 and 11, the allocation of the catalyst in the absence of a functionalized polymer requires a more complex procedure of centrifugation.

Dry catalysts corresponding to the present invention, easily crushed to the state of engineering powders without the need for crushing or grinding using a considerable effort. This contrasts with the process of obtaining the majority of DMC catalysts, which are usually dried to obtain a pellet with subsequent students of turning the dried filter pressey pellet DMC catalysts in powder needed as a rule, severe stage of grinding. The catalysts corresponding to the present invention, easily crushed to the state of engineering powders.

Through polymerization of epoxy compounds catalysts disclosed in this invention have the polyol having a very low degree of unsaturation. As shown in Table 1, typical levels of unsaturation in the case of poly(oxypropylene)diol (molecular weight 8000), resulting in "stressful" conditions at 130oWith make up from 0.004 to 0.007 IEC/year Polyols obtained from the catalysts of the present invention, contain lower levels paleologou tail fractions of high molecular weight and cause less problems associated with gel formation and contamination of the reactor, even in the case where the above-mentioned polyol get into "stress" conditions, for example, at low concentrations of catalyst and under accelerated adding epoxysilane. As shown in Table 1, the catalyst obtained without adding functionalized polymer, if used in a "stress" conditions (20 ppm of catalyst and 2-hour adding propylene oxide) (see Comparative Example 11), ensures p is th fraction of high molecular weight (9260 ppm polyol, having a maximum molecular weight exceeding 100,000) and significant contamination of the reactor due to gel formation. The catalysts corresponding to the present invention allows to overcome these problems by obtaining polyols having a low viscosity, low tail fractions of high molecular weight and does not contaminate the reactor even in "stressful" conditions.

It is quite obvious that the key receipt of DMC catalysts with high activity is inhibition of education vysokokritichnyh forms mentioned catalysts. Despite the fact that over the decades to get polyepoxide compounds used DMC catalysts having a relatively high degree of crystallinity, DMC catalysts having a relatively high degree of crystallinity, now it has become clear that more desirable DMC catalysts having a relatively low degree of crystallinity. The present invention provides a General method of obtaining essentially non-crystalline catalysts. The inclusion in the composition of the catalyst functionalized polymer provides reception, essentially non-crystalline catalyst is of abalioglu high quality.

The present invention includes a method of obtaining the above-mentioned catalysts. The said method comprises the reaction of aqueous solutions of metal salt and metal cyanide in the presence of organic complexing agent and a functionalized polymer.

In a typical method, aqueous solutions of metal salt (e.g. zinc chloride) and cyanide metal (for example, hexacyanocobaltate potassium) initially react in the presence of organic complexing agent (for example, tert-butyl alcohol) and functionalized polymer with an effective stirring to obtain a suspension of the catalyst. Salt of the metal used in excess. The above suspension of the catalyst comprises the reaction product of metal salt and metal cyanide, which is a double metallocyanide connection. There is also an excess of metal salt, water, an organic complexing agent and a functionalized polymer; a part of each of them are included in the structure of the catalyst.

Mentioned reactive substances together with any required temperature. The above-mentioned catalyst, in a preferred embodiment, receiving at a temperature in the range of about SUP>oWith up to approximately 60oC.

Mentioned organic complexing agent and the functionalized polymer can be included in any or both of an aqueous solution of salt or added to a suspension of the catalyst immediately after the deposition of the DMC compound. Preference is usually given prior to mixing the complexing agent with either or with both aqueous solutions before combining the reacting substances. If, instead, mentioned complexing agent is added to the mentioned draft of the catalyst, then the reaction mixture should be stirred using a homogenizer or mixer with large shear effort to obtain the most active forms of the above-mentioned catalyst. Preference is usually given to adding the aforementioned functionalized polymer after deposition of the DMC compound. After that, the catalyst containing polymer, as a rule, isolated from the suspension of catalyst in any appropriate way, for example, filtration, centrifugation, decantation, etc.,

Selected solid catalyst containing polymer, in a preferred embodiment, washed with an aqueous solution, the content is functionalized polymer. After washing the above-mentioned catalyst, in the preferred embodiment, generally dried under vacuum until such time as the said catalyst reaches a constant weight. Suitable methods of washing and selection of the above-mentioned catalyst is described in U.S. patent 5482908, the description of which reference is incorporated into this description.

The present invention includes a method of obtaining polyepoxides connection. This method involves the polymerization of epoxysilane in the presence of double metallocyanide catalyst corresponding to the present invention. Among the preferred epoxy compounds include ethylene oxide, propylene oxide, butene oxides, styrene oxide, etc., and mixtures thereof. The above method can be used to obtain statistical or block copolymers. Polyepoxides connection may be, for example, polyetherpolyols obtained through polymerization of epoxysilane in the presence of an initiator containing a hydroxyl group.

In the above method corresponding to the present invention, to obtain polyepoxide compounds of other types, can include other monomers that will copolymerize, who must register using conventional DMC catalysts can be obtained with these catalysts disclosed in this invention. For example, epoxysilane copolymerized with oxetane (as described in U.S. patent 3278457 and 3404109) for the formation of polyethers or anhydrides as described in U.S. patent 5145883 and 3538043) for the formation of polyesters or of simple and complex polyether polyols. Getting polyethers, polyesters, simple and complex polyether polyols using double metallocyanide catalysts are fully described, for example, in U.S. patents 5223583, 5145883, 4472560, 3941849, 3900518, 3538043, 3404109, 3278458, 3278457 and in the work of Tolkien.L. Suharto (J. L. Schuchardt) and S. D. Harper (S. D. Harper) SPI Proceedings. 32nd Annual Polurethane Tech./Market. Conf. (1989) 360. Descriptions of these U.S. patents relating to the synthesis of polyols using DMC catalysts, in full included as reference in the present description.

The polyether polyols (or monali), obtained using the catalysts of the present invention, in the preferred embodiment, have, on average, approximately from 1 to 8 hydroxyl functional groups, in the preferred embodiment, approximately, from 2 the variant, have srednekislye molecular weight in the range of about 500 to about 50000. A more preferred range is about 1000 to about 12000; most preferred is the range of about 2000 to about 8000.

The following examples serve as a simple illustration of the present invention. Specialists in the art will be apparent, numerous variations within the spirit of the present invention and its scope defined by the attached claims.

EXAMPLE 1

Obtaining catalyst: the complex hexacyanocobaltate zinc/ t-butyl alcohol containing poly(N,N-dimethylacrylamide)

Get a 5% (wt. ) solution of poly(N,N-dimethylacrylamide) in distilled water (Solution 1). To obtain a solution of 2 zinc chloride (75 g) dissolved in distilled water (275 ml) and t-butyl alcohol (50 ml). To a solution of zinc chloride are added 50 grams of Solution 1. A solution of 3 get by dissolving hexacyanocobaltate potassium (7.5 g) in distilled water (100 ml). Solution 3 is added to a mixture of zinc chloride/poly(N,N-dimethylacrylamide) for 30 minutes to homogenize the mixture with 20% magnago coil, intended for heating or cooling, is maintained at the 50oC. the Intensity of mixing in the next 10 minutes, increased to 40%. The resulting mixture was filtered under pressure through a 5 micron filter at a pressure of 40 pounds/inch2(excessive pressure 2,812 kg/cm2). The resulting filter pressnow cake resuspended in a mixture of t-butyl alcohol (200 ml) and distilled water (70 ml), the mixture obtained is homogenized at 40% intensity mixing for 10 minutes and again filtered under pressure, as described earlier. The obtained solid substance resuspended in t-butyl alcohol (185 ml), repeat the washing process and selection. The resulting filter pressnow cake is dried in a vacuum oven at 60oC to constant weight. Dry the catalyst was easily crushed to svobodnago powder. In the composition of the obtained catalyst is 24% (wt.) poly(N,N-dimethylacrylamide). The activity of the catalyst relative to the polymerization of propylene oxide is 23,8 g RO/min at 100 ppm catalyst.

EXAMPLE 2

Obtaining catalyst: the complex hexacyanocobaltate zinc/ t-butyl alcohol containing poly(1-vinyl pyrrolidone)

For polucheniya Solution 2 hexacyanocobaltate potassium (7.5 g) dissolved in distilled water (100 ml). A solution of 3 get by dissolving poly(1-vinylpyrrolidone) (8.0 g) in water (50 ml) and t-butyl alcohol (2.0 ml). Solution 2 is added to Solution 1 over 30 minutes from the homogenization of the mixture with 20% of the maximum intensity of mixing. The temperature of the reaction mixture during the above addition is maintained at the 50oC. the Intensity of mixing in the next 10 minutes, increased to 40%. The homogenizer stop. To the above mixture add a Solution of 3, the resulting mixture with a magnetic stirrer stirred for 3 minutes, and then filtered under pressure through a 20-micron filter at a pressure of 40 pounds/inch2. The resulting filter pressnow cake resuspended in a mixture of t-butyl alcohol (130 ml) and distilled water (55 ml), the mixture obtained is homogenized at 40% intensity mixing for 10 minutes. The homogenizer stop. Add a further quantity of poly(1-vinylpyrrolidone) (2.0 g), the resulting mixture with a magnetic stirrer stirred for 3 minutes, and then filtered under pressure, as described earlier. The resulting filter pressnow cake resuspended in t-butyl alcohol (185 ml) and Polus. Add a further quantity of poly(1-vinylpyrrolidone) (1.0 g) and carry out the mixing, filtering and selection of solid catalyst particles, as described earlier. The resulting filter pressnow cake is dried in a vacuum oven at 60oC to constant weight. Dry the catalyst was easily crushed to svobodnago powder. In the composition of the obtained catalyst is 22% (wt.) poly(1-vinylpyrrolidone). The activity of the catalyst relative to the polymerization of propylene oxide is 12.2 g RO/min at 25 ppm of catalyst.

EXAMPLE 3

Obtaining catalyst: the complex hexacyanocobaltate zinc/ t-butyl alcohol containing copolymer of poly(1-vinylpyrrolidone and acrylic acid

To obtain the Solution 1 solution of zinc chloride (62,5% (wt.) in water (120 g) is mixed with distilled water (230 ml) and t-butyl alcohol (50 ml). To obtain Solution 2 hexacyanocobaltate potassium (7.5 g) dissolved in distilled water (100 ml). A solution of 3 get by dissolving a copolymer of poly(1-vinylpyrrolidone) and acrylic acid (8.0 g) in water (50 ml) and t-butyl alcohol (2.0 ml). Solution 2 is added to Solution 1 for 30 minutes at 50oWith the homogenization of the mixture with 20% of the Mac is up to 40%. The homogenizer stop. To the above mixture add a Solution of 3, the resulting mixture with a magnetic stirrer stirred for 3 minutes, and then filtered under pressure through a 20-micron filter at a pressure of 40 pounds/inch2. The resulting filter pressnow cake resuspended in a mixture of t-butyl alcohol (130 ml) and distilled water (55 ml), the mixture obtained is homogenized at 40% intensity mixing for 10 minutes. The homogenizer stop. The resulting mixture was filtered under pressure, as described earlier. The resulting filter pressnow cake resuspended in t-butyl alcohol (185 ml) and the resulting mixture is homogenized at 40% intensity mixing for 10 minutes. The homogenizer stop. Filtering and selection of solid catalyst particles is carried out, as described earlier. The resulting filter pressnow cake is dried in a vacuum oven at 60oC to constant weight. Dry the catalyst was easily crushed to svobodnago powder. In the composition of the obtained catalyst is 24% (wt.) copolymer of poly(1-vinylpyrrolidone and acrylic acid. The activity of the catalyst relative to the polymerization of propylene oxide costal is Baltata zinc/ t-butyl alcohol, containing poly(vinylethylene ether)

Get 8,0% (wt.) a solution of poly(vinylethylene ether) in distilled water (Solution 1). To obtain a solution of 2 zinc chloride (37.5 g) and 10 grams of Solution 1 is mixed with distilled water (137,5 ml) and t-butyl alcohol (25 ml). To obtain a solution of 3 hexacyanocobaltate potassium (3.75 g) dissolved in distilled water (50 ml). A solution of 4 get by mixing 17 g of Solution 1 with t-butyl alcohol (1.0 ml). Solution 3 is added to a Solution of 2 within 15 minutes at 50oWith the homogenization of the mixture with 20% of the maximum intensity of mixing. The intensity of mixing in the next 10 minutes, increased to 40%. The homogenizer stop. To the above mixture add a solution of 4, the resulting mixture with a magnetic stirrer stirred for 3 minutes, and then filtered under pressure through a 20-micron filter at a pressure of 40 pounds/inch2. The resulting filter pressnow cake resuspended in a mixture of t-butyl alcohol (65 ml) and distilled water (27.5 ml), the mixture obtained is homogenized at 40% intensity mixing for 10 minutes. The homogenizer stop. Add additional kaisaki stirred for 3 minutes. The resulting mixture was filtered under pressure, as described earlier. The resulting filter pressnow cake resuspended in t-butyl alcohol (92,5 ml) and the resulting mixture is homogenized at 40% intensity mixing for 10 minutes. The homogenizer stop. Filtering and selection of solid catalyst particles is carried out, as described earlier. The resulting filter pressnow cake is dried in a vacuum oven at 60oC to constant weight. Dry the catalyst was easily crushed to svobodnago powder. In the composition of the obtained catalyst is 8,0% (wt.) poly(vinylethylene ether). The activity of the catalyst relative to the polymerization of propylene oxide is 25 g RO/min at 25 ppm of catalyst. The Figure 1 presents the x-ray powder diffraction pattern of the above-mentioned catalyst.

EXAMPLE 5

Obtaining catalyst: the complex hexacyanocobaltate zinc/ t-butyl alcohol containing poly(vinylethylene ether) and polyetherdiol

To obtain a solution of 1 zinc chloride (75 g) and poly(vinylethylene ether (3.0 g) dissolved in distilled water (275 ml) and t-butyl alcohol (60 ml). To obtain Solution 2 hexacyanocobaltate potassium (7.5 g) was dissolved in dis the ACCA 1000, 8.0 g) in distilled water (50 ml) and t-butyl alcohol (2.0 ml). Solution 2 is added to Solution 1 for 30 minutes at 50oWith the homogenization of the mixture with 20% of the maximum intensity of mixing. The intensity of mixing in the next 10 minutes, increased to 40%. The homogenizer stop. To the above mixture add a Solution of 3, the resulting mixture with a magnetic stirrer stirred for 3 minutes, and then filtered under pressure through a 20-micron filter at a pressure of 40 pounds/inch2. The resulting filter pressnow cake resuspended in a mixture of t-butyl alcohol (130 ml), distilled water (155 ml) and poly(vinylethylene ether) (1.0 g), the mixture obtained is homogenized at 40% intensity mixing for 10 minutes. The homogenizer stop. Add a further quantity of poly(oxypropylene)diol (molecular weight 1000, 2.0 g) and the resulting mixture with a magnetic stirrer stirred for 3 minutes. The resulting mixture is filtered under pressure, as described earlier. The resulting filter pressnow cake resuspended in t-butyl alcohol (185 ml) and poly(vinylmation ether) (1.0 g) and the resulting mixture is homogenized at 40% into poly(oxypropylene)diol (molecular weight 1000, 1.0 g) and the resulting mixture is stirred using a magnetic stirrer for 3 minutes. Filtering and selection of solid catalyst particles is carried out, as described earlier. The resulting filter pressnow cake is dried in a vacuum oven at 60oC to constant weight. Dry the catalyst was easily crushed to engineering powder. In the composition of the obtained catalyst is 20% (wt.) the combination of poly(vinylethylene ether) and poly(oxypropylene)diol. The activity of the catalyst relative to the polymerization of propylene oxide is 17.9 g RO/min at 25 ppm of catalyst.

EXAMPLE 6

Obtaining catalyst: the complex hexacyanocobaltate zinc/ t-butyl alcohol containing poly(vinylethylene ether) and polyetherdiol

To obtain a solution of 1 zinc chloride (37.5 g) dissolved in distilled water (137,5 ml) and t-butyl alcohol (25 ml). Solution 2 get by dissolving hexacyanocobaltate potassium (3.75 g) in distilled water (50 ml). A solution of 3 get by dissolving poly(oxypropylene)diol (molecular weight 1000, 4.0 g) in distilled water (25 ml) and t-butyl alcohol (5.0 ml). Solution 2 is added to Solution 1 for 15 minutes at 50oWith homogenization on the existing 10 minutes rises to 40%. The homogenizer stop. To the above mixture add a Solution of 3, the resulting mixture with a magnetic stirrer stirred for 3 minutes, and then filtered under pressure through a 20-micron filter at a pressure of 40 pounds/inch2. The resulting filter pressnow cake resuspended in a mixture of t-butyl alcohol (65 ml) and distilled water (27.5 ml) and the resulting mixture is homogenized at 40% intensity mixing for 10 minutes. The homogenizer stop. Add a further quantity of poly(oxypropylene)diol (molecular weight 1000, 1.0 g) and the resulting mixture with a magnetic stirrer stirred for 3 minutes. The resulting mixture is filtered under pressure, as described earlier. The resulting filter pressnow cake resuspended in t-butyl alcohol (92,5 ml) and poly(vinylethylene ether) (3.0 g) and the resulting mixture is homogenized at 40% intensity mixing for 10 minutes. The homogenizer stop. Add a further quantity of poly(oxypropylene)diol (molecular weight 1000, 0.5 g) and the resulting mixture is stirred using a magnetic stirrer for 3 minutes. Filtering and selection of solid catalyst particles carry the th mass. Dry the catalyst was easily crushed to svobodnago powder. In the composition of the obtained catalyst is 18% (wt. ) a combination of poly(vinylethylene ether) and polyetherdiol. The activity of the catalyst relative to the polymerization of propylene oxide is 21.7 g RO/min at 25 ppm of catalyst.

EXAMPLE 7

Obtaining catalyst: the complex hexacyanocobaltate zinc/ t-butyl alcohol containing polyetherpolyols

To obtain the Solution 1 solution of zinc chloride (62,5% (wt.) in water, 120 g) is mixed with distilled water (230 ml) and t-butyl alcohol (50 ml). To obtain Solution 2 hexacyanocobaltate potassium (7.5 g) dissolved in distilled water (100 ml). A solution of 3 get by dissolving LEXOREZ 1080-55 polyol(condensation polymer of 2-methyl-1,3-propane diol and adipic acid, the product of the company Inolex Chemical Co., 8.0 g) in water (50 ml) and t-butyl alcohol (2.0 ml). Solution 2 is added to Solution 1 for 30 minutes at 50oWith the homogenization of the mixture with 20% of the maximum intensity of mixing. The intensity of mixing in the next 10 minutes, increased to 40%. The homogenizer stop. To the above mixture add a Solution of 3, the resulting mixture with Marie excess pressure of 40 pounds/inch2. The resulting filter pressnow cake resuspended in a mixture of t-butyl alcohol (130 ml) and distilled water (55 ml) and the resulting mixture is homogenized at 40% intensity mixing for 10 minutes. The homogenizer stop. Add more polyetherpolyols (2.0 g) and the resulting mixture with a magnetic stirrer stirred for 3 minutes. The resulting mixture is filtered under pressure, as described earlier. The resulting filter pressnow cake resuspended in t-butyl alcohol (185 ml) and the resulting mixture is homogenized at 40% intensity mixing for 10 minutes. The homogenizer stop. Add more polyetherpolyols (1.0 g) and the resulting mixture is stirred using a magnetic stirrer for 3 minutes. Filtering and selection of solid catalyst particles is carried out, as described earlier. The resulting filter pressnow cake is dried in a vacuum oven at 60oC to constant weight. Dry the catalyst was easily crushed to svobodnago powder. In the composition of the obtained catalyst is 5.0 percent (wt.) polyetherpolyols. The activity of the catalyst relative to the polymerization of propylene oxide is 19,2 ATA zinc/t-butyl alcohol, containing poly(1-vinyl pyrrolidone)

To obtain the Solution 1 solution of zinc chloride (120 g 62,5% (wt.) Zn12in water) dissolved in distilled water (230 ml) and t-butyl alcohol (50 ml). Solution 2 get by dissolving hexacyanocobaltate potassium (7.5 g) in distilled water (100 ml). A solution of 3 get by mixing poly(1-vinylpyrrolidone) (8.0 g) with distilled water (50 ml) and t-butyl alcohol (2.0 ml). Solution 2 is added to Solution 1 for 30 minutes at 50oWith the homogenization of the mixture with 20% of the maximum intensity of mixing. The intensity of mixing in the next 30 minutes increased to 40%. The homogenizer stop. To the above mixture add a Solution of 3, the resulting mixture with a magnetic stirrer stirred for 3 minutes, and then filtered under pressure through a 20-micron filter at a pressure of 40 pounds/inch2. The resulting filter pressnow cake resuspended in a mixture of t-butyl alcohol (130 ml) and distilled water (55 ml) and the resulting mixture is homogenized at 40% intensity mixing for 10 minutes. The homogenizer stop. Add a further quantity of poly(1-vinylpyrrolidone) (trout under pressure, as described previously. The resulting filter pressnow cake resuspended in t-butyl alcohol (185 ml) and the resulting mixture is homogenized at 40% intensity mixing for 10 minutes. The homogenizer stop. Filtering and selection of solid catalyst particles is carried out, as described earlier. The resulting filter pressnow cake is dried in a vacuum oven at 60oC to constant weight. Dry the catalyst was easily crushed to svobodnago powder. In the composition of the obtained catalyst is 22% (wt.) poly(1-vinylpyrrolidone). The activity of the catalyst relative to the polymerization of propylene oxide is 14.7 g RO/min at 20 ppm of catalyst.

COMPARATIVE EXAMPLE 9

Obtaining catalyst: the complex hexacyanocobaltate zinc/ t-butyl alcohol containing polyetherpolyols

To obtain a solution of 1 zinc chloride (283,5 g) dissolved in distilled water (1039 ml) and t-butyl alcohol (189 ml). Solution 2 get by dissolving hexacyanocobaltate potassium (28,35 g) in distilled water (378 ml). A solution of 3 get by mixing poly(oxypropylene)diol (molecular weight 1000, 30,2 g) with distilled water (180 ml) and t-butyl alcohol (7E adding the frequency mixing for 1 hour increase up to 900 rpm at a pressure of nitrogen, 10 pounds/inch2(0,703 kg/cm2). After that, the frequency mixing is reduced to 450 rpm, add a Solution of 3, and the resulting mixture is stirred for 3 minutes. Solid substances are by filtration under pressure through a 20-micron filter at a pressure of 40 pounds/inch2. The resulting filter pressnow cake resuspended in a mixture of distilled water (201 ml) and t-butyl alcohol (492 ml) and the resulting mixture is stirred with a frequency of 900 rpm for 1 hour. The frequency mixing is reduced to 450 rpm and add a further quantity of poly(oxypropylene)diol (molecular weight 1000, 7.6 g). After stirring for 3 minutes, the solids emit, as described earlier. The resulting filter pressnow cake resuspended in t-butyl alcohol (700 ml) and the resulting mixture is stirred at a frequency of 900 rpm for 1 hour. The frequency mixing is reduced to 450 rpm and add a further quantity of poly(oxypropylene)diol (molecular weight 1000, 3.8 g). After stirring for 3 minutes, the solid is isolated and dried under vacuum at 60oC to constant weight. Dry the catalyst was easily crushed to svobodnago powder. Activity catalysis of Alena x-ray powder diffraction pattern of the above-mentioned catalyst.

COMPARATIVE EXAMPLES 10 AND 11

Obtaining catalyst: the complex hexacyanocobaltate zinc/ t-butyl alcohol obtained without functionalized polymer

To obtain the Solution 1 hexacyanocobaltate potassium (8.0 g) is dissolved in distilled water (300 ml) and t-butyl alcohol (50 ml). Solution 2 get through dissolution of zinc chloride (75 g) in distilled water (75 ml). Solution 2 is added to Solution 1 over 30 minutes from the homogenization of the mixture with 20% of the maximum intensity of mixing. After complete addition, the resulting mixture was homogenized for 10 minutes with 40% of the maximum intensity of mixing. The above mixture was centrifuged at 17000 rpm for 30 min for separation of solids. The obtained solid substance resuspended in a mixture of t-butyl alcohol (155 ml) and distilled water (55 ml). The resulting mixture is homogenized at 40% intensity mixing for 10 minutes, then centrifuged as previously described. The obtained solid substance resuspended in t-butyl alcohol (185 ml), the mixture obtained is homogenized at 40% intensity mixing for 10 minutes and release. The resulting catalyst is dried under vacuum current powder.

The activity of the catalyst relative to the polymerization of propylene oxide amounts to 17.9 g/min at 50 ppm of catalyst (Comparative Example 10) and 9.3 g RO/min at 20 ppm of catalyst (Comparative Example 11). The Figure 1 presents the x-ray powder diffraction pattern of the above-mentioned catalyst.

AN EXAMPLE OF A

Polymerization of epoxy compounds: experiments with the definition of speed is the common procedure

In a 1-liter reactor equipped with a mixer, make Polyoxypropylenediamine (molecular weight 700) starter (70 g) and containing the polymer catalyst, hexacyanocobaltate zinc (from 0,0114 to 0,057 g, 20-100 ppm in the finished polyol). The resulting mixture is stirred, heated to 105oWith and evaporated under vacuum to remove trace quantities of water from trilogo starter. The pressure in the reactor is brought to a vacuum, comprising approximately 30 inches of RT. Art. (7.62 mm RT. Art.) and one portion add the propylene oxide (10-11 g). Then carefully control the pressure in the reactor. An additional portion of propylene oxide added only after the reactor will happen accelerated pressure drop; the pressure drop indicates the activation of the catalyst. After checking activation Katie reactor was maintained at the level of approximately 10 pounds/inch2. After complete addition of the propylene oxide, the temperature of the resulting mixture is kept at level 105oTo establish a constant pressure. Then from Paleologo product under vacuum to remove residual amounts of unreacted monomer, polyol cool and emit.

To determine the rate of passage of the reaction, draw a graph of the dependence of rate of RO (g) duration of response (min). The index of maximum steepness of the slope of the curve represents the rate of reaction in the number of grams of RO undergoing transformation within minutes. The intersection of said line and a horizontal line, which is a continuation of the baseline curve is taken as the induction time (in minutes) required for the activation of the catalyst. The measured rate of reaction is summarized in the Table.

In the case where the above procedure is used to measure the rate of polymerization of propylene oxide, catalysts corresponding to the present invention, will generally polimerizuet RO with a speed of approximately more than 15 g/min at 20 ppm at 105oC. the Rate of polymerization of epoxy compounds with the use of the project for similar catalysts, but obtained in the absence of a functionalized polymer (see Comparative Example 11).

THE EXAMPLE IN

Synthesis of polyetherpolyols: polyoxypropylene, molecular weight 8000

In a 1-liter reactor equipped with a mixer, make Polyoxypropylenediamine (molecular weight 725) starter (65 g) and the catalyst, hexacyanocobaltate zinc (0,0173 g, 25 ppm). The resulting mixture is stirred, heated to 130oWith and evaporated under vacuum to remove trace quantities of water from delovogo starter. In the reactor, which originally supported a vacuum of about 30 inches of RT.art., add the propylene oxide (12 g), followed by careful control of the pressure in the reactor. An additional portion of propylene oxide added only after the reactor will happen accelerated pressure drop; the pressure drop indicates the activation of the catalyst. After checking the activation of the catalyst gradually over 2 to 6 hours, is added to the remaining propylene oxide (618 g) (see Table). After complete addition of propylene oxide the temperature of the mixture kept at level 130oTo establish a constant pressure. Then from Paleologue 1-8 and Comparative Examples C9-C11).

The preceding examples are given only as illustrations; the scope of the present invention is defined by the following claims.

1. The catalyst, which, according to x-ray powder diffraction, essentially, is not crystalline, and which contains: (a) double metallocyanide connection, (b) an organic complexing agent, and (C) from 2 to 80 wt. % functionalized polymer that (i) has the General structure

< / BR>
where R' is hydrogen, -COOH or1-C5alkyl group; And one or more functional groups selected from the group comprising-OH, -NH2, -OTHER, -NR2, -SH, -SR, -COR, -CN, -Cl, -Br, -C6H4-OH, -C6H4-C(CH3)2OH, -CONH2, -CONHR, -CO-NR2, -OR, -NO2, -NHCOR, -NRCOR, -COOH, -COOR, -CHO, -OCOR, -COO-R-OH, -SO3H, -CONH-R-SO3H, pyridinyl and pyrrolidinyl, where R1-C5alkyl or Allenova group, and where n has a value ranging from 5 to 5000

or (ii) selected from the group composed of polyesters, polycarbonates, polymers oxazoline, polyalkylimide, copolymers of maleic acid and maleic anhydride, hydroxyethyl cellulose, starches and Polyacetals, or water soluble SSA fact, n has a value from 10 to 500.

3. The catalyst p. 1, characterized in that the said double metallocyanide connection includes hexacyanocobaltate zinc.

4. The catalyst p. 1, characterized in that the said organic complexing agent comprises tert-butyl alcohol.

 

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FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.

SUBSTANCE: claimed catalyst includes alumina, mixture of transition metal complexes with nitrogen skeleton ligands (e.g., iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex). According the first embodiment catalyst is prepared by application of homogeneous mixture of transition metal complexes onto substrate. iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex (or vise versa) are alternately applied onto substrate. According the third embodiment catalyst is obtained by mixing of complexes individually applied onto substrate. Method for polyethylene producing by using catalyst of present invention also is disclosed.

EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.

7 cl, 5 tbl, 27 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides catalytic deiodination composition containing 0.95 wt parts of ethyl acetate and 8-50 wt parts of metallic zinc in the form of 3-6 mm granules. Hexafluoro-1,2,3,4-terachlorobutane production process involving use of this catalyst is characterized by that process is carried out for 20-40 h at 20-25°C, after which resulting product is washed with water at ambient temperature. Catalyst is distinguished by being accessible, inexpensive, nontoxic, and easy-to-use. Process is characterized by high yield of hexafluoro-1,2,3,4-terachlorobutane (90-98%) resulting in easiness of isolation thereof using ordinary water washing. Equipment necessities are also non-onerous.

EFFECT: increased yield of desired product and simplified technology.

2 cl, 1 tbl, 9 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides catalytic deiodination composition containing 0.95 wt parts of ethyl acetate and 8-50 wt parts of metallic zinc in the form of 3-6 mm granules. Hexafluoro-1,2,3,4-terachlorobutane production process involving use of this catalyst is characterized by that process is carried out for 20-40 h at 20-25°C, after which resulting product is washed with water at ambient temperature. Catalyst is distinguished by being accessible, inexpensive, nontoxic, and easy-to-use. Process is characterized by high yield of hexafluoro-1,2,3,4-terachlorobutane (90-98%) resulting in easiness of isolation thereof using ordinary water washing. Equipment necessities are also non-onerous.

EFFECT: increased yield of desired product and simplified technology.

2 cl, 1 tbl, 9 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst consists of complex [Nd(NO3)7][C5H5NH]4 constituted by neodymium nitrate, pyridine, and nitric acid taken in molar ratio 1:4:4, respectively.

EFFECT: achieved accessibility of catalyst.

1 tbl, 2 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst consists of complex [La(NO3)7][C5H10NH2]4 constituted by lanthanum nitrate, piperidine, and nitric acid taken in molar ratio 1:4:4, respectively.

EFFECT: achieved accessibility of catalyst.

1 tbl, 2 ex

FIELD: chemical industry; production of catalytic compounds for polymerization of monomers.

SUBSTANCE: the invention is dealt with the field of polymerization of the monomers and with the methods of production of catalytic compounds and compounds, which are applied at polymerization of at least one monomer. The offered methods contain: 1) a treated solid oxide compound produced due to a contact at least of one solid oxide with at least of one compound having an electron-seeking anion; 2)a metallocenes compound of a metal from IVA group; 3) an organoaluminum compound. The technical result: production of a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

EFFECT: the invention allows to produce a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

71 cl, 99 ex, 13 tbl

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