Superior double metallocyanide catalysts and methods for their production

 

(57) Abstract:

Describes a new catalyst, which includes pasty double metallocyanide (DMC) compound, an organic complexing agents and water. It is suitable for the production of epoxy polymers. In the pasty composition of the catalyst is at least about 90 wt.% particles having a size in the range of about from 0.1 to 10 μm, based on measurement results of light scattering in polyetherpolyols dispersions of catalyst particles. Preferred catalysts have a bimodal particle size distribution. Paste the catalyst more active and easier to obtain compared to powdered DMC catalyst. The polyols obtained with a paste-like catalyst, have a low degree of unsaturation, low viscosity and narrow limits of the distribution of molecular weights and, in addition, they are suitable for a whole range of polyurethane products. Superior results have been obtained with DMC catalysts powdered form with a very small particle size. 5 C. and 10 C.p. f-crystals, 6 PL.

The invention relates to an improved dual metallocyanide (DMC) catalysts and methods for their preparation. Upamanyu of polyether polyols. The polyether polyols are valuable polymeric intermediates for obtaining foams, elastomers, sealants, coating materials and adhesives.

Background of the invention

Double metallocyanide (DMC) complex compounds are well known catalysts for the polymerization of epoxides. The catalysts exhibit high activity and allow you to get the polyether polyols having a low degree of unsaturation compared with similar polyols obtained using the master (e.g., KOH) catalyst. Polyols with low unsaturation desirable because they provide polyurethanes with excellent value for physical and mechanical properties.

DMC catalysts receive as a result of the reaction of aqueous solutions of salts of metals and cyanides of metals from sediment DMZ connection. A member of the drug include organic complexing agents of low molecular weight, as a rule, ether or alcohol. The complexing agents is incorporated into the structure of the catalyst and active catalyst. In a typical process for preparation of the catalyst precipitated DMZ connection promis by centrifugation or filtration. In conclusion, the catalyst is dried prior to the formation of a solid pellet, usually in a vacuum furnace. After that, the dried catalyst is crushed to obtain svobodnago powder. For the polymerization of epoxides typically use the catalyst in powder form. In U.S. patent N 3829505 and the patent application of Japan N 4-145123 shows the typical ways of obtaining catalysts: each of them includes the details of the process of drying and grinding of the catalyst prior to use.

Van der Hulst (Van der Hulst), and others (U.S. patent N 4477589) discloses a method of obtaining powder DMC catalysts. In addition, in the above-mentioned sources reveals how you can use the suspension DMC catalysts in propoxyethanol glitzerinovm the starter, which eliminates the necessity of selection of the powdered catalyst. In the manufacture of suspension DMC the catalyst is deposited in the usual way. An aqueous mixture of catalyst is treated with an organic complexing agents and suspension of the catalyst, water and complexing agents combined with propoxycarbonyl glycerin. This mixture is desorbed to remove water and excess organic complexing agents, I, which includes about 3 to 5% (wt.) DMC catalyst is used as catalyst in the reaction with additional starter a polyol and propylene oxide to obtain a polyol. Thus, the source mentioned discloses the use as a catalyst powder DMC catalyst or the diluted suspension DMZ connection propoxyethanol glycerine. Despite the obvious advantages of suspension options, powdered catalysts are used much more widely.

Currently in the art known powder DMC catalysts with exceptionally high activity in the polymerization of epoxides. See, for example, U.S. patent N 5470813. However, even the best powder DMC catalysts have some drawbacks. First, the drying of the catalyst after separation requires a considerable investment of time and availability of the vacuum furnace. Drying large quantities of catalyst are particularly burdensome. Secondly, the dried catalyst must be crushed to obtain powder. This stage requires costly crusher, grinder or mill. Both phases expensive from the point of view of capitania and grinding can have a negative impact on the quality and characteristics of the catalyst. Excessive heat during drying can lead to decomposition of the catalyst and reduce its activity. Heating of the catalyst due to friction during grinding may also have a negative impact on the characteristics of the catalyst. Changes in conditions of grinding and drying from batch to batch can cause the volatility characteristics of the catalyst and changes in the quality of polyols.

Required superior double metallocyanide catalysts. Preferred catalysts have a high activity, similar to that described in U.S. patent N 5470813. Especially necessary catalysts that can be obtained without stages of drying or crushing, which greatly affect the overall cost of production. Especially valuable catalyst can be manufactured with improved consistency of performance between the parties and should improve the quality of polyether polyols obtained by using the above catalyst.

Summary of the invention.

The present invention is an improved dual metallocyanide (DMC) catalyst. In the catalyst composition is a paste-like DMZ connection, organic complexalarm, according to measurements by light scattering in polyetherpolyols dispersions of catalyst particles. The preferred paste catalyst corresponding to the present invention includes catalyst particles having a bimodal particle size distribution in the range from 0.1 to 10 microns.

The present invention includes a method of obtaining a paste-like catalyst. Water-soluble metal salt and a water-soluble metal cyanide react in the presence of organic complexing agents with the formation of a suspension of the catalyst. The suspension is washed with an aqueous solution of the organic complexing agents. Ultimately produce a paste catalyst, which includes DMC compound, complexing agents and water.

Pasty catalysts corresponding to the present invention, provide a cause of surprise and valuable advantages in comparison with powdered catalysts that are typically used in the art. First, the process of preparation of the catalyst easier. Because excluded stages of drying and grinding, for a shorter time and with lower costs can be obtained catalysis is s have a number of advantages in obtaining polyols. The surprisingly high activity provides the ability to quickly obtain polyols with very low levels of catalyst. The resulting polyols have a more narrow distribution of molecular weights and lower viscosity compared with polyols obtained by using powdered DMC catalysts. And, finally, the polyols obtained by the above-mentioned catalysts, allow you to get the prepolymers of low viscosity, easily machinable, and polyurethanes with excellent value for physical and mechanical properties.

Detailed description of the invention

In the pasty composition of the catalysts of the present invention, includes dual metallocyanide (DMC) compound, an organic complexing agents and water. Double metallocyanide compounds suitable for 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 vam variant represents an anion, chosen from the group composed of a halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate. The value of n is from 1 to 3 and satisfies the valence state of M. examples of suitable metal salts include, but are 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 suitable for the present invention, in the preferred embodiment, have the General formula (Y)aM'(CN)b)(A)cwhere M' is chosen from the group which 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). Water-soluble metal cyanide may include one or more of these metals. In the above formula Y - ion alkaline or alkaline earth metal. A is an anion selected from the group which is at and nitrate. Both a and b are integers greater than or equal to 1; the sum of charges a, b and C balances the charge of M'.

The number of suitable water-soluble cyanides of metals include, but not limited to, potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III), lithium hexacyanoferrate(III), etc. are examples of double 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(III) etc. Additional examples of suitable double metallocyanide compounds listed in U.S. patent N 5158922, the description of which is included in the present description by reference.

Catalytic compositions corresponding to the present invention produced in the presence of complexing agents. In General, the complexing agents should be relatively soluble in water. Suitable complexing agents are known in the art, as disclosed, for example, in U.S. patent N 5158922. The complexing agents add or% the introduction of complexing agents in DMC complex may play a crucial role. As a rule, use excessive amounts of complexing agents. Preferred complexing agents are water-soluble organic compounds, which include heteroatom, can form complex compounds 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. Among the preferred complexing agents are water-soluble aliphatic alcohols selected from the group which consists of ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, verboselevel alcohol and tributyl alcohol. Most preferred is tributyl alcohol.

In the catalyst composition also includes water. The required amount is the amount of water, sufficient to make a paste of the desired consistency. Water and organic complexing agents are usually included even in the structure of the powder DMC catalysts; each of them into a paste-like catalysts of the present invention, there is essentially much the Beaulieu water into a paste-like catalysts, relevant to the present invention, may vary within a very wide range. In a preferred embodiment, the composition of the paste of the catalyst is from 10 to 60% (wt.) DMC compounds, from about 1 to 20% (wt.) water, and the rest is organic complexing agents. In a more preferred pasty catalysts is from 15 to 40% (wt.) DMZ connection, from 5 to 15% (wt.) water, and the rest is organic complexing agents.

Unlike powdered DMC catalysts known in the art, pasty DMC catalysts corresponding to the present invention, include, which is a feature of at least 90% (wt.) particles having a size in the range from 0.1 to 10 μm, based on measurement results of light scattering in polyetherpolyols dispersions of catalyst particles. In a preferred embodiment, the paste contains at least 90% (wt.) particles having a size in the range from 0.1 to 5 μm.

Preferred pasty catalysts corresponding to the present invention, have a bimodal particle size distribution in the range from 0.1 to 10 μm, based on measurement results of light scattering in polyetherpolyols dispersions of particles kaleelah from 1 to 10 μm, and a smaller portion of the particles having a size in the range from 0.1 to 0.5 μm. Larger particles in the preferred embodiment have a size in the range from 1 to 5 μm and smaller particles in the preferred embodiment have a size in the range from 0.15 to 0.4 μm.

Even larger particles pasty catalyst, however, is much smaller in General than the typical particles of powdered catalyst. Large particles of powder catalysts can be caused by aggregation of smaller particles as complexing agents and water are removed in the drying process. In the preferred composition pasty catalysts is composed of a small number, if included at all, particles larger than about 4 microns. Powdered DMC catalysts known in the art, are particles of larger size, typically in the range of about 5 to 600 μm. In addition, the distribution of powdered DMC catalysts is generally unimodal character within a 5-to 10-micron range. The main fraction of the particles of the powdery catalyst has a size greater than 100 microns.

To measure the sizes of particles n is the updated measure, dispersional first pasty catalyst polyetherpolyols (molecular weight approximately less than 1000, see Example G) with subsequent measurement of the size of particles in this dispersion by means of light scattering. In one of the suitable methods use particle analyzer MICROTRAC X100 (company Leeds & Northrup), which measures the static properties of the light scattering particles. This device can be used to approximate the relative amounts of fine and coarse particles in a paste-like catalysts.

Very small catalyst particles (for example, particles having a size less than about 0.5 μm) are often much easier to analyze using quasielastic light scattering (QLS). This method, which measured the dynamic properties of the scattering particles, has been used successfully to verify and particle size distribution of very fine catalyst particles in the sample. QLS are easy to make on the suspension of catalyst particles in the polyol of low molecular weight. For example, to obtain measurements QLS is possible to use a suspension of 5% (wt.) DMC catalyst dipropyleneglycol. The MICROTRAC method is generally more suitable for determining otnositelnye, known in the art, generally have a particle size in the range of about 5-600m μm, unimodal distribution in the range of 5-10 μm and undetectable number of very small particles. In contrast, pasty catalysts corresponding to the present invention, contain at least approximately. 90% (wt.) particles having a size in the range of about from 0.1 to 10 μm, based on measurement results of light scattering in polyetherpolyols dispersions of catalyst particles. Preferred pasty catalysts also have a bimodal particle size distribution.

The invention includes methods of manufacturing paste-like catalysts. In General, a paste catalyst can be produced from the "scrapings" either through recovery powder DMC catalyst. Both methods are described below and in Examples A and C.

According to one of the methods of the present invention and illustrates an example of A water-soluble metal salt and a water-soluble metal cyanide react in the presence of organic complexing agents with the formation of a suspension of the catalyst. The suspension was washed with water dissolve the allocate those pasty catalyst, which includes DMC compound, an organic complexing agents and water. In the composition mentioned paste is at least 90% (wt. ) particles having a size in the range from 0.1 to 10 μm, based on measurement results of light scattering in polyetherpolyols dispersions of catalyst particles. In a preferred embodiment, the composition of the paste will be from 10 to 60% (wt. ) DMC compounds, from 1 to 20% (wt.) water, and organic complexing agents - the rest.

Aqueous solutions of metal salt and metal cyanide must be thoroughly mixed by means of homogenization, mixing with high shearing force, etc.,) and to respond, as disclosed in U.S. patent N 5470813, the description of which is included in the present description by reference. Organic complexing agents may be included in either or both of an aqueous solution of salt or it may be added to DMZ connection immediately after deposition of the catalyst. In a preferred embodiment, the organic complexing agents before thorough mixing of the reagents are pre-mixed with either water-soluble metal salt or a water-soluble metal cyanide, or with both. Premixing guarantees dostatochnosti get DMC catalyst, having the required particle size and activity, and often eliminates the need for homogenization or mixing with high shearing force. The method of pre-mixing is further described in the application for the European patent N 0743093.

An important difference methods of the present invention, from the previously proposed methods of preparation of the catalyst, is how outstanding pasty catalyst. In the foregoing methods of preparation of the catalyst described wyszukiwania catalyst after washing and selection for solid pellet. Wet residues of the catalyst is usually heated in a vacuum oven to remove excess water and organic complexing agents. After that, the dried catalyst was ground to obtain svobodnago powder. The stages of drying and grinding are revealed throughout the literature and are discussed, for example, in U.S. patent N 3829505 and the patent application of Japan N 4-145123.

To our surprise, we found that the stages of drying and grinding mainly from the process of preparation of the catalyst are removed. Paste the catalyst is not just acceptable, as a catalyst for the polymerization of epoxides: often he obespechitelnoj form. First, the process of preparation of the catalyst easier. Because excluded two stage drying and grinding, the catalysts have been received within a shorter period of time and with lower costs. Secondly, the present invention eliminates the large capital cost of drying ovens and blenders. Thirdly, the obtained catalysts of higher quality because it reduces the decomposition of the catalyst, which can occur either during drying or during grinding. Fourthly, the present invention provides for obtaining catalysts with relatively reproducible particle size compositions; this feature minimizes the differences in catalyst activity between the parties and increases to maximum consistency between batches of polyether polyols made from the catalysts. Finally, the present invention provides a highly active catalysts suitable for the manufacture of high-quality polyether polyols. None of these benefits pasty DMC catalysts should not be of the prototypes, which indicates the need for drying and grinding DMC catalysts and their use in poroshkoobraznoe is making a "restored" paste from powdered DMC catalyst and organic complexing agents. Also optional is added to water. Can be used any way of recovery; however, it is important to mix the powdered DMC catalyst with organic complexing agents for the preparation of the catalyst, in which the particles have the desired size and a bimodal distribution. In accordance with one of the preferred ways powdered DMC catalyst vigorously mixed with organic complexing agents and water to produce a slurry of the recovered catalyst. Next, produce a paste catalyst, which includes DMC compound, an organic complexing agents and water. Pasta includes catalyst particles having a bimodal particle size distribution in the range from 0.1 to 10 μm, based on measurement results of light scattering in polyetherpolyols dispersions of catalyst particles. Examples 16 and 17 (table 4) illustrate the above method. As table 4 shows, pasty DMC catalysts obtained through recovery like pasty catalysts made from "scraping", provide excellent results in the synthesis of polyols.

The present invention cluto is combined with the starter polyol, for example, polyoxypropyleneamine ARCOL PPG-425, PPG-725 or PPG-1025 (products company ARCO Chemical Company), etc., and well stirred until formation of a suspension of the catalyst. This mixture can decorrelates to remove volatile materials if necessary. Starter polyol in the preferred embodiment, has a nominal hydroxyl number of functional groups in the range of 2 to 8 and srednekamennogo molecular weight in the range from about 200 to 2000. The suspension in the preferred embodiment, has a solids content of catalyst in the range from 1 to 20% (wt.), in a more preferred from 5 to 15% (wt. ). In the following mentioned suspension can be used as a catalyst to obtain polyether polyols. Examples 18-20 (table 5) show how to obtain a suspension DMZ of the catalyst paste of the catalyst. The method of producing polyols of example F can be used to obtain a polyol of the suspension DMC catalyst. As the results in table 5, using suspensions DMC catalyst obtained from pastes, get diols (molecular weight 8000) low viscosity, narrow distributions of molecular weight and very low degrees of unsaturation.

We substania powder DMC catalysts and use only the smallest particles. Particularly superior results are obtained with powdered DMC catalysts in which at least 90% (wt.) particles can pass through a standard sieve USA N 230 (63 μm). As the results, presented in table 6, whole powder DMC catalyst (Comparative example 7) initiates the polymerization (becomes active) for 7 min under standard reaction conditions (see Example F) and ensures polyoxypropylene (molecular weight 8000), having a viscosity 3480 FTAs, which consists of visible particulate catalyst suspended in diola having a molecular weight of 8000. In contrast, the sample powder DMC catalyst, which passes through the sieve N 230 (63 μm), initiates the polymerization faster (within 5 min) and provides pure diol (molecular weight 8000), low viscosity (3260 cSt) and narrow molecular weight distribution (Mw/Mn = 1,14). Interestingly, the catalyst passing through the sieve (N) 140 (0,104 mm) and stays on the N 200 sieve (0.074 mm) (Comparative example 24), does not exceed the composite material or in relation to the time of initiation, nor the quality of polyol.

The present invention includes a method polucheniyami of the invention: paste the recovered paste, suspension or sifted powder. The preferred epoxides are ethylene oxide, propylene oxide. the butene oxide, styrene oxide, etc., and mixtures thereof. The process can be used to obtain statistical or block copolymers. Epoxy polymer can be, for example, polyetherpolyols obtained by polymerization of epoxide in the presence of initiator, which includes a hydroxyl group.

In the process according to the present invention, to obtain an epoxy polymers of other types can include other monomers that will copolymerisate with the epoxide in the presence of DMZ connection. Any of the copolymers known in the art, obtained using a conventional DMC catalysts can be obtained using the catalysts of the present invention. Epoxides, for example, copolymerized with oxetane (as disclosed in U.S. patent N N 3278457 and 3404109) to obtain polyesters or with anhydrides (as disclosed in U.S. patent N N 5145883 and 3538043) to obtain a complex of the polyester or simple and complex polyether polyols. Obtaining a polyether, a complex of the polyester and simple and complex polyetherpolyols the 883, 4472560, 3941849, 3900518, 3538043, 3278458 and in the work of Tolkien.L. Shewhart (J. L. Schuchardt) and S. D. Harper (S. D. Harper), SPI Proceedings, 32nd Annual Polyurethane Tech./Market.Conf. (1989) 360. Descriptions of all of the above U.S. patents relating to the synthesis of polyols using DMC catalysts included in the present description by reference.

Pasty catalysts corresponding to the present invention, highly active and like catalysts, disclosed in U.S. patent N 54708134, sufficiently active for use in extremely low quantities. At levels of catalyst components 50, 25 or less parts per million (ppm), it can often be left in the polyol, eliminating the need for final cleaning. As table 2 shows, pasty DMC catalysts are clear advantages compared to even the best powder catalysts. For the same amount of catalyst paste catalyst initiates faster and provides polyol with the best properties, including lower viscosity, more narrow distribution of molecular weight and high purity. As table 3 shows, pasty DMC catalysts suitable for the popular masses even in the case when the time of the filing of propylene oxide (PO) significantly reduced. Compare the polyols of Example 11 (a paste catalyst, the duration of the feed RO 6 h) with polyols of Comparative example 12. These results demonstrate the advantages pasty DMC catalysts compared with the best known powder DMC catalysts.

Polyols made from the catalysts of the present invention have a low viscosity. In turn, the polyurethane prepolymers made from these polyols also have a relatively low viscosity, which makes them easier machinability. The polyurethane foams, sealants, elastomers and coating materials obtained from polyols and prepolymers, have a great blend of physical and mechanical properties, which is a consequence of a low degree of unsaturation, low viscosity and a narrow distribution of molecular masses of these polyols.

The following examples merely illustrate the present invention: specialists in the art will be apparent, numerous variations that can be made within the spirit of the present invention and the amount of points attached formula izobreteny/BR> B round bottom flask with a capacity of 1 l, equipped with a mechanical stirrer, additional funnel and a thermometer, make distilled water (604 g), potassium hexacyanocobaltate (14.8 g) and tributyl alcohol (78 g). The mixture is stirred to dissolve all salts of cobalt. The resulting solution is heated to 30oC. for 50 min with stirring, a solution of zinc chloride in water (50% (wt.) zinc chloride, 304 g of solution). Stirring is continued for 30 min at 30oC. the Resulting white suspension centrifuged. The wet cake of solid particles is separated and resuspended with active stirring in a solution of butyl alcohol (204 g) and water (112 g). The complete suspension of all solids in the wash solution, the mixture is stirred for 30 minutes, the Suspension is again centrifuged and the wet solids are separated. Solid particles resuspended 99.5% tributyl alcohol (288 g), centrifuged and exhale, as described earlier. In the past includes about 24% (wt.) complex compounds of zinc hexacyanocobaltate, the rest is tributyl alcohol (about 64% (wt. ) and water (about 12% (wt.)). A sample of this paste-like catalyst is used "as the doctrine of powdery catalyst based on zinc hexacyanocobaltate

Sample pasty catalyst obtained in example A, is transformed into a dry powder as follows. Sample pasty catalyst is dried to constant weight in a vacuum oven at 45oC. the Obtained solid brittle dry mass is crushed using a mortar and pestle to obtain svobodnago powder. A sample of this powder catalyst used for the synthesis of polyol. Cm. tables 1-3 and 6.

17 Example C

Getting restored pasty DMC catalyst from powder

A sample of the catalyst of Comparative example B (powdered catalyst) in turn restored pasty catalyst as follows. A suspension of powdered catalyst (33% (wt.)) in t-butyl alcohol is prepared by combining and homogenizing the components. Add water (10% (wt.)) and the mixture is homogenized by means of a quick vigorous stirring. The slurry thickens to a paste-like consistency. The paste is used "as is" as a catalyst for the synthesis of polyol. Cm. table 4.

Example D

Getting suspension DMC catalyst of pasty catalyst

A sample of the catalyst of example A about serout at low speed to obtain a suspension of the catalyst in a homogeneous distribution, which includes about 10% (wt.) solid particles. This mixture of liquid and solid particles from it easily deposited. The suspension was stripped under vacuum (20-30 mm Hg) to remove volatile materials at low temperature (40-45oC; temperature low enough to prevent deactivation of the catalyst). The composition of the resulting suspension of catalyst is 13.7 percent (wt. ) solids. Suspension liquid; over time there was a visible slight settling of solid particles. The suspension of catalyst used "as is" as a catalyst for the synthesis of polyol.

Similarly suspended catalyst is obtained using ARCOL PPG-725 (polyoxypropylene, a molecular weight of 760 or PPG-1025 (polyoxypropylene, molecular weight 1000). both products company ARCO Chemical Company. Desorbed suspension of PPG-725 diol is liquid, while the suspension of PPG-1025 diol is more like a paste. Each of these suspensions is used "as is" as a catalyst for the synthesis of polyol. Cm. table 5.

Example E

Getting sifted DMC catalyst

Clumps of powdery catalyst based on zinc hexacyanocobaltate obtained as the I U.S. standard sieve trays (according to the specifications of the American society of testing materials E-11). Screen trays and accessories are in the following order (top to bottom): cover, sieve No. 50 (0,297 mm) sieve N 100 (0,149 mm) sieve (N) 140 (0,104 mm) sieve 200 N (0,074 mm) sieve N 230 (0,063 mm) sieve N 325 (0,044 mm) sieve No. 400 (0.038 mm), the bottom tray. Stack installed on the vibrating screen model RX-24 (product Tyier Industries) and shaken for 30 minutes, the Sample remaining on each sieve are used as catalysts for the synthesis of polyol. Cm. table 6.

Example F

Getting polyoxypropylene (molecular weight 8000): the General procedure

B reactor with a capacity of 2 gallons (7,571 liters) contribute polyoxypropylene ARCOL PPG-725 (molecular weight of 760, 618 g) and a complex catalyst based on zinc hexacyanocobaltate/butyl alcohol (paste, powder, restored paste or suspension; amounts presented in tables 2-6). The reactor was rinsed several times with dry nitrogen. The mixture is stirred and the reactor vacuum (2 pounds/square inch (0,141 kg/square centimeter)). The stirred mixture is heated to 130oC. Add the propylene oxide (72 g). Additional propylene oxide is administered only after a rapid pressure reduction in the reactor, indicating activation of the catalyst. After you add the rest of propylene oxide (5810 R). After complete addition of propylene oxide mixture is maintained at a temperature of 130oC for 1 h Residual amount of unreacted propylene oxide is removed from the polyol under vacuum. After that, the polyol is cooled to 80oC and removed from the reactor. Define the properties of the obtained polyoxypropylene having a molecular weight of about 8000 (property, see tables 2-6).

Example G

Obtaining samples for analysis of particle size on the installation MICROTRAC X-100

Suspension 250 ppm of catalyst based on zinc hexacyanocobaltate in polyoxypropylene (PPG-725 diol, molecular weight of 725) was prepared as follows. A sample of catalyst (paste or powder, 0.15 g in terms of dry catalyst) is placed on the surface of 25 g of PPG-725 diol in the beaker. (When using paste of catalyst required amount of paste is 0.15 g, divided by% (wt.) DMC catalyst paste). In chemical glass adds extra PPG-725 diol (125 g). The contents are well stirred with a mechanical mixer until a homogeneous dispersion of solid particles in the polyol. After that, the suspension of catalyst added with additional mixing 450 g of PP are given only as illustrations. Following claims define the scope of the present invention. The

1. The catalyst for polymerization of epoxy compounds, which includes dual metallocyanide (DMC) connection, characterized in that the catalyst contains pasty double metallocyanide compound, an organic complexing agents and water, is pasty and it includes at least 90 wt.% particles having a size in the range from 0.1 to 10 μm, based on measurement results of light scattering in polyetherpolyols dispersions of catalyst particles.

2. The catalyst p. 1, wherein at least 90 wt.% catalyst particles have a size in the range from 0.1 to 5 μm.

3. The catalyst p. 1, characterized in that it comprises particles having a size in the range from 0.1 to 0.5 μm, judging by the results of measurement of quasi-elastic light scattering in polyetherpolyols dispersions of catalyst particles.

4. The catalyst PP.1, 2 or 3, characterized in that the particles have a bimodal particle size distribution in the range from 0.1 to 10 μm

5. The catalyst p. 4, characterized in that a large proportion of catalyst particles has a size in the range from 1 to 10 μm, and Manisha stuudy points, characterized in that it comprises from 10 to 60 wt.% DMC compounds, from 1 to 20 wt.% water and organic complexing agents rest.

7. The catalyst according to any one of the preceding paragraphs, characterized in that DMC compound is zinc hexacyanocobaltate.

8. The catalyst according to any one of the preceding paragraphs, characterized in that the organic complexing agents is tributyl alcohol.

9. The catalyst according to any one of the preceding paragraphs, characterized in that it is capable of polimerizuet the propylene oxide (PO) with a speed of more than 3 g/minute at a concentration level of 100 ppm catalyst, calculated on the weight of finished polyether, at 105°C.

10. The catalyst according to any one of the preceding paragraphs, characterized in that the recovery paste powder DMC catalyst, water, and organic complexing agents.

11. The method of preparation of the catalyst according to any one of paragraphs.1-10, including: (a) reacting a water-soluble metal salt and water-soluble metal cyanide in the presence of organic complexing agents with the formation of a suspension catalyst, wherein (b) suspension of the catalyst is washed with water races who have pasty catalyst, which includes DMC compound, an organic complexing agents and water.

12. The method of preparation of the catalyst according to any one of paragraphs.1-10, characterized in that exercise (a) mixing powdered DMC catalyst with organic complexing agents with the formation of the suspension of recovery of the catalyst and (b) the allocation of pasty catalyst, which includes DMC compound, an organic complexing agents and water.

13. The method according to p. 12, characterized in that the powder DMC the catalyst is mixed with an organic complexing agents and water in step (a).

14. The suspension of catalyst for polymerization of epoxy compounds comprising a catalyst containing double metallocyanide (DMC) connection and starter polyol, characterized in that the catalyst contains a paste catalyst according to any one of paragraphs.1-10 or obtained by the method according to PP.11, 12 or 13.

15. Powdery catalyst for the polymerization of epoxy compounds containing double metallocyanide (DMC) connection, characterized in that the catalyst obtained from a paste of the catalyst according to any one of paragraphs.1-10 and has at least 90 wt.% part of the polymer by the polymerization of epoxy compounds in the presence of a catalyst, characterized in that the use of the catalyst according to any one of paragraphs.1-10 and 15 or obtained by the method according to PP.11, 12 or 13.

 

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The invention relates to polymeric films comprising at least one layer made of a copolymer of ethylene or ternary copolymer of ethylene

The invention relates to a technology for obtaining a polymer of olefins and their use in polymer alloys and molded articles, in particular metallocene catalyst and method for producing a copolymer of cycloolefin, and also to polymeric alloy and molded product comprising at least one copolymer of cycloolefin

The invention relates to new multi-core metallocene compounds of the formula I, in which M1denotes a metal of group IVб of the Periodic system of the elements; X is a halogen atom; L and L1are the same or different and represent a substituted cyclopentadienyl, optionally substituted indenyl and unsubstituted fluorenyl; denotes a group of formula (a), in which R1denotes a divalent hydrocarbon bridging group, the residues R2are the same and denote WITH1-C4is an alkyl group; M2denotes the silicon, as well as the way they are received, containing the catalytic system, a method for producing a polyolefin and a polymer molded product

The invention relates to a new organoboron compound having catalytic activity, of the formula I

[RjM-Xd-MRj]a-bAc+(I)

in which R are, independently of one another, identical and denote C1-C40alkyl; X is, independently from each other, equal or different and denote C1-C40alkyl; M is, independently of one another, identical or different and denote an element of IIIa, IVa, Va group of the Periodic system of elements, provided that one M is boron, a is a cation of an element Ia, IIa and IIIa groups of the Periodic system of elements, carbene-hydronium - or sulfonyl - cation or compound Quaternary ammonium, and a is an integer from 0 to 10, b is an integer from 0 to 10, C is an integer from 0 to 10 and a = C; d is 1; j is an integer from 1 to 3

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: 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: polymerization catalysts.

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

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

16 cl, 1 tbl, 3 ex

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: industrial organic synthesis.

SUBSTANCE: polyetherpolyols are synthesized via reaction of diols or polyols with ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof in presence of suspended multimetallic cyanide complex catalyst in reactor provided with stirrer, wherein reaction mixture is recycled with the aid of pump through externally located heat-exchanger.

EFFECT: increased productivity based on unit volume in unit at high quality of product.

9 cl, 4 ex

FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention relates to a methyl ethyl ketone production process via catalytic oxidation of n-butenes with oxygen and/or oxygen-containing gas. Catalyst is based on (i) palladium stabilized with complexing ligand and (ii) heteropolyacid and/or its acid salts, in particular molybdo-vanado-phosphoric heteropolyacid having following composition: H11P4Mo18V7O87 and/or acid salt Na1.2H9.3Mo18V7O87, said complexing ligand being notably phthalocyanine ligand. Catalyst is regenerated by making it interact with oxygen and/or oxygen-containing gas at 140-190°C and oxygen pressure 1 to 10 excessive atmospheres. Oxidation of n-butenes is conducted continuously in two-stage mode at 15 to 90°C in presence of above-defined catalyst.

EFFECT: enhanced process efficiency due to increased stability of catalyst resulting in considerably increased productivity and selectivity.

7 cl, 1 dwg, 3 tbl, 8 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: polymerization processes and catalysts.

SUBSTANCE: alkylene oxide polymerization is conducted in presence of catalyst based on bimetallic cyanide complex and initiator containing hydroxyl group. Al last part of the catalyst is preliminarily subjected to treatment by ultrasonic and/or electromagnetic emission. Invention discloses both polymerization catalyst treatment method and catalyst itself.

EFFECT: enabled production of polyether-polyols with low unsaturation level and increased activity of catalyst.

10 cl, 3 ex

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