Method of alkoxylation of the organic compounds in the presence of the new framework materials

FIELD: chemical industry; methods of production of the polyethers of the aliphatic alcohol.

SUBSTANCE: the invention is pertaining to the method of production of the polyethers of the aliphatic alcohol by alkoxylation of the organic compounds by alkoxylation of the organic compounds with the alkoxylating agent, which is selected from the mono- or multipurpose epoxides having from 2 up to 30 atoms of carbon and the mono- or multipurpose polyesterpolyols having the molecular mass about 600 g/mole, or their mixtures in the presence of the catalytic system, which includes the organometallic framework material containing the pores and, at least, one ion of the metal, and, at least, one bidentate organic compound, which is coupled with the indicated ion of the metal by the coordination bond. At that the ion of the metal is selected from ions of the elements of the groups Ia, IIa, IIIa, IVa up to VIIIa and Ib up to VIb of the Periodic system, and the bidentate organic compound is selected among the substituted or un substituted aromatic polycarboxylic acids which may contain one or several atomic nuclei and the substituted or unsubstituted aromatic polycarboxylic acids, which contain, at least, one heteroatom and which may have one or several kernels. The given method allows to produce the polyethers of the aliphatic alcohols having the small amounts of the impurities, in particular, of the low molecular substances having the intensive odor and which does not include the complex stages of refining of the source materials and-or the intermediate products. The produced polyethers of the aliphatic alcohols are used for production of the polyurethane by interaction of such polyether of the aliphatic alcohol, at least, with one isocyanate.

EFFECT: the invention allows to produce the polyethers of the aliphatic alcohols having the small amounts of the impurities, the low molecular substances with the intensive odor, which does not include the complex stages of refining of the source materials and-or the intermediate products.

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The present invention relates to a method of alkoxysilane organic compounds in the presence of catalytic systems containing metal-organic framework material comprising pores and a metal ion, and at least bidentate organic compound, and mentioned bidentate organic compound is associated with the metal ion coordination bond. The invention also encompasses an integrated way to obtain polyurethanes from diisocyanates and polyether aliphatic alcohol or modified polyethers of aliphatic alcohols, which were obtained using the method of alkoxysilane according to the present invention. Moreover, this invention relates to polyurethanes obtained by the method in accordance with the invention, as well as molded articles containing polyurethanes obtained according to the invention.

The polyurethanes obtained in accordance with the invention, particularly suitable for the production of polyurethane foams, polyurethane cast films and elastomers.

Polyurethane properties such as mechanical properties and smell, are very dependent on isocyanate and polyether aliphatic alcohols, which are respectively used to receive them, and not necessarily from the initiators used. A particularly strong effect for the tion on the properties of the resulting polyurethane has a structure polyether aliphatic alcohol. In turn, properties of polyethers of aliphatic alcohols strongly influenced by the way they are received and especially the properties and the method of obtaining raw materials. A detailed description of this phenomenon can be found in WO 01/7186 and DE 10143195.3 of this application. As other sources of prior art relating to the receipt of polyether aliphatic alcohol, mention should be made of WO 01/16209 and WO 00/78837.

The decrease in the number of impurities in the process of getting polyethers of aliphatic alcohols and/or polyurethanes is of considerable interest for their various uses. Automotive and furniture industry require increasing the number of polyurethanes, which possibly do not emit substances that have a smell. In accordance with the standards of Daimler Chrysler, specified as PB VWL 709, dated January 11, 2001 requires that the volatile matter of the parts used inside the vehicle, do not exceed 100 ppm, and the allocation of condensed substances, respectively, do not exceed 250 hours/million

Impurities present in the polyurethanes also adversely affect their mechanical properties. Impurities and side effects in many cases lead to monofunctional products. The functionality of polyetherols and mechanical properties of polyurethanes, such as elongation, tensile strength, R is sriv and stiffness, in General deteriorate.

Polyethers of aliphatic alcohols can be obtained, for example, catalyzed by a base or acid polyaddition of oxides of alkali metals to polyfunctional organic compounds (starters, initsiatoram). Suitable starters are, for example, water, alcohols, acids or amines, or a mixture of two or more components. Such methods of obtaining are particularly disadvantageous for the reason that you need several complex stages of purification to separate the remainder of the catalyst from the reaction product. In addition, with increasing chain length of the resulting polyether polyols and the content of the monofunctional products and substances with a strong smell, which is undesirable in polyurethane production increases.

Reduced functionality is particularly damaging for elastomers as used polyethers of aliphatic alcohols should be largely bifunctional. In the presence of monofunctional impurities in simple aliphatic polyester alcohol functionality is reduced below 2, which is manifested in a significant deterioration in the mechanical properties of polyurethanes, particularly tensile strength and elongation.

In addition, by-products resulting from side reactions occurring in the process is e reaction catalyzed by a base or acid, partly contained in the polyurethane in the form of impurities with a smell. Especially should be mentioned aldehydes, for example, propionic aldehyde, cycloacetal, allyl alcohol and the products of their reactions. Automotive and furniture industry need to increase the use of polyether polyols and polyurethanes having low odor or no odor at all.

Therefore, the object of the invention is to develop a method of producing polyether aliphatic alcohols, polyurethanes, respectively, which leads to the production of polyethers of aliphatic alcohols and, accordingly, of polyurethanes, with small amounts of impurities, in particular, low molecular weight substances having an intense smell, and which does not include complex stages of purification of raw materials and/or intermediates.

This problem is solved by the method of alkoxysilane organic compounds, which lies in the interaction of at least one organic compound, which is capable of alkoxylates at least one alkoxylation agent in the presence of a catalytic system, which will get a simple polyester aliphatic alcohol. This method is characterized by the fact that the catalytic system includes metalloorganic the ski frame material, containing pores, and at least one metal ion and at least one bidentate organic compound, which is associated with the said metal ion coordination bond. In addition, the task is solved in an integrated way to obtain polyurethane, which includes at least the following stages:

(2) the interaction of at least one organic compound, which is capable of alkoxylates at least one alkoxylation agent through the process described above, which is easy polyester aliphatic alcohol;

(3) the interaction polyether aliphatic alcohol with stage (2)at least one isocyanate.

As alkoxygroup agent at the stage (2) is preferably used mono - or multifunctional epoxide having from two to 30 carbon atoms, or mono - or multifunctional polyether polyols having a molar weight of about 600 g/mol, or a mixture of two or more agents. In particular, the use of substituted or unsubstituted alkilinity having from two to 24 C-atoms, such as alkalinity having as substituents halogen, a hydroxyl group, an acyclic ether group or ammonium. As suitable compounds should be mentioned as examples: ethylene oxide, 1,2-epoxypropane, 1,2-shall ethyl-2-methylpropan, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-methyl-3-methylbutane, 1,2-epoxybutane, 1,2-methyl-3-methylpentan, 1,2-epoxyhexane, 1,2-epoxyethane, 1,2-epoxyoctane, 1,2-Apoksiomen, 1,2-epoxydecane, 1,2-Apoksiomen, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxycyclohexane, (2,3-epoxypropyl)benzene, vinyloxy, 3 phenoxy-1,2-epoxypropane, 2,3-apoximately ether, 2,3-apoximately ether, 2,3-apoximately ether, 2,3-epoxy-1-propanol, (3,4-epoxybutene)stearate, 4,5-epoxypolyester, 2,3-epoxypropyl, 2,3-epoxypropanol, glycidylether, methylglycine, ethyl-2,3-epoxybutane, 4-(trimethylsilyl)butane-1,2-epoxide, 4-(triethylsilyl)butane-1,2-epoxide, 3-(performer)propanone, 3-(perforated)propanone, 3-(performatic)propanone, 4-(2,3-epoxypropyl)morpholine, 1-(oxiran-2-ylmethyl)pyrrolidin-2-he a mixture of two or more compounds.

Especially should include: aliphatic 1,2-alkylenes having 2 to 4 C-atoms, such as ethylene oxide, 1,2-butylenes, 2,3-butylenes or isobutylene, aliphatic 1,2-alkilinity having from 5 to 24 C-atoms, cycloaliphatic alkylenes, such as cipointernet, cyclohexanone or cyclododecatriene-(1,5,9)-monoxide, analiticheskii alkylenes, such as styrene oxide.

Special preference in the framework of the present invention is given to ethylene oxide, propylene oxide, 1,2-what epoxybutane, 2,3-epoxybutane, styrene oxide, minilateral and any mixtures of two or more of these substances, in particular ethylene oxide, propylene oxide and mixtures of ethylene oxide, 1,2-epoxypropane.

As polyethers of aliphatic alcohols in the framework of the present invention is particularly use polyether polyols and modified polyether polyols which can be obtained by using the ethylene oxide or propylene oxide, and which can be obtained in accordance with stage (1), mainly according to a variant implementation, described in General terms below. Next stage (1) of the present invention to illustrate is described in detail using as an example of propylene oxide:

Typically, the propylene oxide can be obtained by the interaction of propylene with oxygen; hydrogen and oxygen; hydrogen peroxide; organic hydroperoxides or halohydrin, preferably, by reacting propylene with hydrogen peroxide, more preferably, the interaction of propylene with hydrogen peroxide in the presence of a catalyst containing a zeolite material, especially the interaction of propylene with hydrogen peroxide in the presence of a catalyst comprising a titanium-containing zeolite material having a CS-1 structure.

As hydroperoxides, especially suitable for epoxidation in a hundred is AI (1), it should be noted the hydrogen peroxide. It can be obtained or outside the reaction according to (1) or on the basis of hydrogen and oxygen in situ in the reaction according to (1), respectively.

Thus, the present invention also relates in a preferred embodiment of the method of alkoxysilane organic compounds and integrated method for producing a polyurethane, respectively, where the hydroperoxide used in stage (1)is hydrogen peroxide.

Epoxidation in accordance with stage (1) in principle it is known, for example, from DE 10055652.3 and other patent applications of the applicant, such as DE 10032885.7, DE 10032884.9, DE 10015246.5, DE 19936547.4, DE 19926725.1, DE 19847629.9, DE 19835907.1, DE 19723950.1, relevant parts of which are fully covered by the present application. By epoxidation according to stage (1) receive the propylene oxide of high purity. In particular, the propylene oxide obtained in this way, discovers content6connections <1 hour/million

In the framework of the present invention under the C6connections see, for example, the following compounds: 2-methylpentane, 4-methylpentene-1, n-hexane, hexene, such as 1-hexene, and the components with 6 C-atoms, and, in addition, one or more functional groups selected from the class of aldehydes, carboxylic acids, alcohols, ketones and ethers. In addition, Nigel the more impurities are derivatives of propane, especially chlorinated derivatives of propane, acetaldehyde, propionic aldehyde, acetone, dioxolane, allyl alcohol, pentane, methylpentan, furan, hexane, hexene, methoxypropan and methanol.

The propylene oxide obtained according to stage (1), may further contain other side of the components to 100 hours/million, especially up to 40 hours/million methanol and up to 10 hours/million, mainly before 4 PM/million acetaldehyde.

Compared with other known methods for producing propylene oxide, which are not excluded from this application and that, for example, described in Weissermel, Arpe "Industrielle Organische Chemie" (Industrial organic chemistry), publ. VCH, Weinheim, 4th ed., str-318, with the preferred options stage embodiment (1) according to the invention lead to the formation of propylene oxide, having only a small amount of impurities With6components and does not contain chlorinated organic impurities.

A summary of the above-mentioned prior art and technique to obtain polyethers of aliphatic alcohols on the basis of propylene oxide are given in DE 10143195.3.

Regarding receipt of ethylene oxide, which can also serve as alkoxylation agent and which can also be obtained before conducting the process alkoxysilane organic compounds capable of alkoxycarbonyl, it is broadly disclosed in U.Onken, Anton Behr, "Chemsche Prozesskunde", volume 3, Thieme, 1996, str-305 and Weissermel, Arpe "Industrial Organic Chemistry", 5th ed., Wiley, 1998, str-181.

In the reaction leading to the formation of polyethers of aliphatic alcohols, alkoxylate agent, obtained according to stage (1), in particular, propylene oxide, can be directly used in the reaction according to stage (2). However, it is also possible within the framework of the present invention to alkoxylate agent, in particular the propylene oxide obtained in accordance with stage (1), pre-processed, for example purified. As a method of purification include purification by distillation. Suitable methods are disclosed, for example, in EP-0557116.

Alkoxylate agent obtained in stage (1), in particular, propylene oxide, may be used in this invention alone or together, at least one other alkoxylation agent, especially together, at least one other alkalization.

To obtain a polyether aliphatic alcohol according to stage (2) is possible in the framework of the present invention used in place of or in addition to propylene oxide all alkoxygroup agents, especially alkalisation, which are known to experts in this field, especially the above-mentioned compounds.

In cases where in addition to alkoxylate agent obtained in accordance with stage (1), persons who NGOs of propylene oxide, use at least one other alkoxylate agent, in particular a different accelerated, in the framework of the present invention it is possible to use a mixture of alkoxylated agent, obtained according to stage (1), particularly of propylene oxide, and at least one other alkoxylate agent, in particular accelerated. However, in the present invention it is also possible to alkoxylate agent, obtained according to stage (1), especially propylene oxide, and at least one other alkoxylate agent, especially accelerated, was added later.

Polyethers of aliphatic alcohols, obtained according to stage (2), may, for example, contain also block structure. The structure of the polyether aliphatic alcohols can be adjusted within wide limits by appropriate reaction conditions. Suitable conditions for the reaction according to stage (2) are, for example, the conditions described in WO 99/16775.

Polyethers of aliphatic alcohols obtained in accordance with stage (2)can be modified for the reaction according to stage (3). With regard to such modified polyethers of aliphatic alcohols, especially should mention grafted polyether polyols, in particular those produced by polymerization of styrene and Acrylonitrile in the presence of polya is Aralov; dispersion of politician (PHD polyols), which is produced by interaction of diisocyanates and diamines in the presence of polyetherols; and polyaddition products of the polyisocyanates to the polyols (PIPA polyols), which is produced by interaction of diisocyanates and aminoalcohols in the presence of polyetherols.

The reaction according to stage (2) is carried out in the presence of catalytic systems.

The catalytic system used according to the invention at the stage (2), includes frame material containing ORGANOMETALLIC pores which, in turn, contain a metal ion and at least bidentate organic compound mentioned bidentate organic compound is associated with the metal ion coordination bond. Such a catalytic system essentially known and described, for example, in US 5648508, EP-A-0709253, J.Sol. State Chem.,152(2000) p.3-20, Nature402(1999), str and forth, Topics in Catalysis9(1999), p.105-111, Science291(2001), str-23. An inexpensive way of obtaining them is the subject of the application DE 10111230.0. The content of the above-mentioned literature that there is a link on the contents of this application.

ORGANOMETALLIC frame material used in the present invention, contains pores, in particular micro - and/or mesopores, and micropores are defined as pores having a diameter of 2 nm or lower is, and mesopores - pores having a diameter in the range of from above 2 nm to 50 nm, respectively, according to the definition given in Pure Applied Chem.45, p.71 and forth, in particular, p.79 (1976). The presence of micro - and/or mesopores can be monitored by measuring the absorption to measure the ability of ORGANOMETALLIC frame materials to absorb nitrogen at 77 K according to DIN 66131, 66134. Form type I isotherm curve indicates the presence of micropores. In the preferred embodiment, the specific surface area, calculated according to the Langmuir model (DIN 66131, 66134), is preferably above 5 m2/g, more preferably above 50 m2/g, especially above 500 m2/g and can grow up to over 2000 m2/year

As the metal components in the frame material used according to the invention, special mention should be made of metal ions of elements of groups Ia, IIa, IIIa, IVa to VIIIa and Ib to VIb of the Periodic system; among them are particularly worth noting Mg, CA, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, TA, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, TI, Si, Ge, Sn, Pb, As, Sb and Bi, more preferably Zn, Cu, Ni, Pd, Pt, Ru, Rh and Co. As metal ions of these elements are especially worth mentioning: Mg2+, CA2+, Sr2+, Ba2+Sc3+, Y3+, Ti4+, Zr4+, Hf4+, V4+, V3+, V2+, Nb3+TA3+, Cr3+Mo 3+, W3+, Mn3+, Mn3+, Mn2+That Re3+That Re2+, Fe3+, Fe2+, EN3+, EN2+Os3+Os2+, Co3+, Co2+Rh2+Rh+Ir2+Ir+, Ni2+, Ni+Pd2+Pd+Pt2+Pt+, Cu2+, Cu+Ag+Au+, Zn2+Cd2+Hg2+, Al3+, Ga3+In3+Tl3+Si4+Si2+Ge4+Ge2+Sn4+Sn2+, Pb4+, Pb2+, As5+, As3+, As+, Sb5+, Sb3+, Sb+and Bi5+Bi3+Bi+.

In respect of the preferred metal ions and additional details on them, in particular, reference: EP-A 0790253, especially, p.10, I. 8-30, section "metal Ions", which is included here as a reference.

As at least bidentate organic compound which can form a coordination bond with a metal ion, can be used in principle all compounds which are suitable for this purpose and which satisfy the above requirements to be at least bidentate. The organic compound must have at least two centers, which can form a coordination bond with metal ions metal salt, especially with metals of the above-mentioned groups. With regard to at least bidentate organic is about connection, special mention should be made of compounds having

i) the structure of the alkyl group having from 1 to 10 carbon atoms,

ii) the structure of the aryl group, having from 1 to 5 phenyl rings,

iii) the structure of the alkyl - or arylamine containing alkyl groups having from 1 to 10 carbon atoms, or aryl groups, having from 1 to 5 phenyl rings, these substructures have associated therewith at least one at least bidentate functional group "X", which is covalently linked to the substructure mentioned connection, and where X is selected from the group including:

CO2N, CS2H, NO2, SO3H, Si(OH)3, Ge(OH)3, Sn(OH)3, Si(SH)4, Ge(SH)4, Sn(SH)3, RHO3H, AsO3H, AsO4H, P(SH)3, As(SH)3CH(RSH)2With(PSH)3CH(RNH2)2With(RNH2)3CH(ROH)2With(ROH)3CH(RCN)2With(RCN)3where R is alkyl group having from 1 to 5 carbon atoms, or aryl group containing from 1 to 2 phenyl rings, and CH(SH)2With(SH)3CH(NH2)2C(NH2)2CH(OH)2With(OH)3CH(CN)2and C(CN)3.

Special mention should be made of substituted or unsubstituted mono - or polynuclear aromatic di-, tri - and tetracarbonyl acid and a substituted or unsubstituted aromatic containing at least the, one heteroatom, an aromatic di-, tri - and tetracarbonyl acids that have one or more nuclei.

The preferred ligand is 1,3,5-benzotriazole acid (TSA), particularly preferred metal ions are Co2+and Zn2+.

In addition, at least bidentate organic compounds frame material used in accordance with the present invention may also contain one or more monodentate ligands, which mainly come from the following monodentate compounds:

A. the bonds alkylamines and their respective alkylammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms (and their corresponding ammonium salt);

b. arylamine and their respective allmovie salts, having from 1 to 5 phenyl rings;

C. alkylphosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

d. arylphosphonate salts, having from 1 to 5 phenyl rings;

E. alkylolamides acid and the corresponding alkylolamides anions (and salts), containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

f. allergenicity acids and their corresponding allowances the f anions and salts, having from 1 to 5 phenyl rings;

g. aliphatic alcohols containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

h. akrilovye alcohols having from 1 to 5 phenyl rings;

i. inorganic anions from the group including:

sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrophosphate, diphosphate, triphosphate, postit, chloride, chlorate, bromide, bromate, iodide, Iodate, carbonate, bicarbonate and the corresponding acids and salts of the above-mentioned inorganic anions,

j. ammonia, carbon dioxide, methane, oxygen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1-2-dichloroethane, methylene chloride, tetrahydrofuran, ethanolamine, triethylamine and triftormetilfullerenov acid.

Further details relating to the at least bidentate organic compounds and monodentate compounds which are ligands of the frame material used in the present invention can be taken from EP-A 0790253, the relevant contents of which are incorporated into the present application as reference.

Especially preferred within the present invention are frame materials described herein that contain as metal ion Zn2+and as bidentate compounds whether the Andes, derived from terephthalic acid, which are known in the literature as MOF-5.

Other metal ions and at least bidentate organic compounds and monodentate substances which are respectively suitable for receiving the frame material used in the present invention, and methods for their preparation disclosed in detail in EP-A 0790253, US 5648508 and DE 10111230.0.

As solvents which are particularly suitable for MOF-5, in addition to the solvents disclosed in the above literature, can be used dimethylformamide, diethylformamide and N-organic separately in combination with one another or in combination with other solvents. In the process of receiving frame materials, especially in the process of getting MOF-5, solvents and uterine solutions re-use after crystallization in order to reduce costs and materials.

Department of frame materials, in particular MOF-5, from the mother liquor of crystallization can be achieved by methods known in this field, such as the separation of solid - liquid, for example, centrifugation, extraction, filtration, membrane filtration, filtration cross-flow, flocculation using flocculation auxiliary substances (non-ionic, cationic and anionic auxil athelny substances), or by adding additives that alter the pH, such as salts, acids or bases, by flotation, spray drying or granulation by spraying, or by evaporation of the mother liquor at elevated temperature and/or vacuum and concentration of solids.

The separated frame materials, in particular MOF-5 can or compound, to melt, to ekstradiroval, coextrudable, extruding, roll, foam and pelletized according to methods known in the field of plastics processing.

At stage (2) according to the invention alkoxylate agent, in particular a propylene oxide from step (1) or a mixture of propylene oxide from step (1) and at least one other accelerated, interacts with an organic compound capable of alkoxycarbonyl (organic compound).

In the framework of the present invention in principle can be used all organic compounds that can be alkoxysilane. As a particularly suitable organic compounds should be mentioned the following: water, organic mono - or dicarboxylic acids, such as acrylic acid, methacrylic acid, succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N,N - and N,N'-dialkylamino diamines, having the e from 1 to 4 carbon atoms in the alkyl group, such as optionally mono - or dialkylamino the contrary, Diethylenetriamine, Triethylenetetramine, 1,3-Propylenediamine, 1,3 - or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine were, phenylenediamine, 2,3-,2,4 - and 2,6-toluenediamine and 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane, alkanolamine, such as ethanolamine, N-methyl - and N-acylethanolamine, dialkanolamine, such as diethanolamine, N-methyl - and N-ethyldiethanolamine, and trialkanolamines, such as triethanolamine, and ammonia and multivalent alcohols, such as monoethylene glycol, propandiol-1,2 and -1,3, diethylene glycol, dipropyleneglycol, butanediol-1,4, hexanediol-1,6, glycerin, trimethylolpropane, pentaerythritol, sorbitol and sucrose. The preferred polyether polyols are used, the addition products of ethylene oxide and/or propylene oxide and water, monoethylene glycol, diethylene glycol, propane diol-1,2, dipropyleneglycol, glycerol, trimethylolpropane, Ethylenediamine, triethanolamine, pentaerythritol, sorbitol and/or sucrose alone or in mixture with one another.

Organic compounds can also be used in the form of alkoxylates, especially those which have a molecular weight of Mwin the range from 62 to 15000 g/mol.

In addition, can also be used macromolecule having a functional group with active hydrogen atoms, such as hydrox the global group, especially those mentioned in WO 01/16209.

Polyethers of aliphatic alcohols obtained in stage (2)can react with isocyanates at stage (3). Stage (3) can be carried out directly after stage (2). It is also possible that additional stage, in particular cleaning stage, could be carried out between stages (2) and (3).

In the framework of the present invention can be used one or more isocyanates. In addition to the polyether aliphatic alcohols, obtained according to stage (2), in the reaction according to stage (3) can optionally be used by other components having groups which are reactive toward isocyanates, in particular those that have a hydroxyl group.

As additional IT components can be used, for example, polyesters, other polyethers, Polyacetals, polycarbonates, polyether polyesters and similar connections.

Suitable polyether polyols can be obtained by the interaction of organic dicarboxylic acids having from 2 to 23 carbon atoms, preferably aliphatic dicarboxylic acids having from 4 to 6 carbon atoms, polyhydric alcohols, preferably dialami, respectively, having from 2 to 12 carbon atoms, preferably the t 2 to 6 carbon atoms. As dicarboxylic acids preferably can be used as follows:

succinic acid, glutaric acid, adipic acid, cork acid, azelaic acid, sabotinova acid, decanedicarbonitrile acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. Dicarboxylic acids can be used individually or in mixtures with one another. Instead of the free dicarboxylic acids can also be used the corresponding derivatives of dicarboxylic acids, such as dicarboxylic ecrire alcohols having from 1 to 4 carbon atoms, or anhydrides of dicarboxylic acids.

Examples of polyhydric alcohols are:

ethanediol, diethylene glycol, 1,2 - and 1,3-propandiol, dipropyleneglycol, 1,4-BU-Tandil, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, glycerin and trimethylolpropane. Preferably use ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol and/or trimethylolpropane. In addition, there may be used esters of polyols derived from lactones, for example, caprolactone or hydroxycarbonate acid, such as a-hydroxypropranolol acid. To obtain esters of organic polyols, for example, aromatic or preferably aliphatic polycarboxylic sour the s and/or their derivatives may be subject to interaction with the polyhydric alcohol in the absence of a catalyst or preferably in the presence of a catalyst for the formation of ester. The reaction is carried out preferably in an inert atmosphere, for example in an atmosphere of nitrogen, carbon monoxide, helium, argon, etc. the Entire reaction is carried out in the melt at temperatures of from 150 to 250°C, preferably from 180 to 220°if necessary, under reduced pressure, to the desired acid number, which is preferably less than 10, more preferably less than 2. In accordance with the preferred embodiment of this reaction, the condensation of the mixture to be subjected to the reaction of formation of ester, is first subjected to the reaction until the acid number of from 80 to 30, preferably from 40 to 30, under normal pressure and at temperatures above followed by polycondensation at a pressure of less than 500 mbar, preferably from 50 to 150 mbar. As a catalyst for the formation of ester, mention should be made of Fe, Cd, Co, Pb, Zn, Sb, Mg, Ti and Sn catalysts in the form of metals, metal oxides and metal salts. However, the polycondensation can also be carried out in the liquid phase in the presence of a diluent and/or azeotropically, such as benzene, toluene, xylene or chlorobenzene, in order to azeotrope to drive off the water formed in the condensation process. For more polyether polyols and organic polycarboxylic acids and/or derivatives of acids and polyhydric alcohols condensedmatter in a molar ratio of 1:1,8, preferably 1:of 1.05 to 1:1,2. The resulting polyetherol show the functionality of preferably from 2 to 4, especially from 2 to 3 and a hydroxyl number of preferably from 22 to 100 mg KOH/g can also be used compounds which are reactive towards isocyanates, such as diols, trioli and/or polyols having a molecular weight of 60 to <400, such as aliphatic cycloaliphatic and/or analiticheskie diols, having from 2 to 14, preferably from 4 to 10 carbon atoms, such as ethylene glycol, propandiol-1,3, decanediol-1,10, o-, m-, p-dihydrocyclopenta, diethylene glycol, dipropyleneglycol and preferably butanediol-1,4, hexanediol-1,6 and bis-(2-hydroxyethyl)hydroquinone; triola, such as 1,2,4-, 1,3,5-trihydroxytoluene, glycol and trimethylolpropane; and low-molecular polyalkylene having hydroxyl groups, such as those obtained by the interaction of accelerated and/or 1,2-propylene oxide with the above dialami and/or trioligy as H-functional compound.

In accordance with the present invention a simple polyester aliphatic alcohol with stage (2) is subjected to interaction with at least one isocyanate. In principle, in the framework of the present invention can be used all isocyanates, which are known to the person skilled in the art. In particular it is necessary to mention the following:

aromatic, analiticheskie, aliphatic and/or cycloaliphatic organic isocyanates, preferably diisocyanates.

Special mention should be made of the following individual compounds:

alkylenediamine having from 4 to 12 carbon atoms in alkalinous group, such as 1,12-dodecanesulfonate, 2-ethylmethanesulfonate-1,4, 2-methylphenothiazine-1,5, tetramethyldisilane-1,4, ester of lysine diisocyanate (LDI) and/or hexamethylenediisocyanate-1,6 (GDI); cycloaliphatic diisocyanates such as cyclohexane-1,3 - and 1,4-diisocyanate, and any mixtures of these isomers, 2,4 - and 2,6-hexahydrotriazine and the corresponding mixtures of isomers, 4,4'-, 2,2'-and 2,4'-dicyclohexylmethane and the corresponding mixtures of isomers, and/or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (IPDI).

In addition, as examples, mention should be made of the following isocyanates:

2,4 - and 2,6-toluenediisocyanate and the corresponding mixtures of isomers, 4,4'-, 2,4'-and 2,2'-diphenylmethanediisocyanate and the corresponding mixtures of isomers, mixtures of 4,4'- and 2,2'-diphenylmethanediisocyanate, polyvinylpolypyrrolidone, mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and polyvinylpolypyrrolidone (crude-MDI) and mixtures of crude-MDI, and toluylenediisocyanate. In addition, can also be used a mixture containing, by KRA the least two of the aforementioned isocyanates. Moreover, can be used, modified isocyanates, with which, biuret, hard-ether, urea, allophanate, carbodiimide, uretdione and/or containing urethane groups, di - and/or polyisocyanates (hereinafter also designated as a modified polyurethane groups).

Among them may be mentioned the following individual compounds:

organic polyisocyanates containing urethane group and having a content of NCO-groups from 50 to 10 wt.%, preferably from 35 to 15 wt.% relative to the total weight, such as 4,4'-diphenylmethanediisocyanate, mixtures of 4,4'- and 2,4'-diphenylmethanediisocyanate, raw(untreated)-MDI or 2,4 - and 2,6-toluylenediisocyanate that are modified accordingly, for example, by using low molecular weight diols, triolo, dialkylglycerol, triacylglycerol or polyoxyethyleneglycol having a molecular weight of up to 6000, especially molecular weight up to 1500 can be used by themselves or in a mixture with one another. As di - or polyoxyethyleneglycol, which, in turn, can also be used individually or in mixtures of one with another, it is necessary to mention the following: dietilen and dipropyleneglycol, polyoxyethylene, polyoxypropylene and polyoxipropylenediamine, trio is s and/or thetruly. In addition, can also be used prepolymers containing NCO groups and respectively having an NCO content of from 25 to 3.5 wt.%, mainly from 21 to 14 wt.%, respectively, of the total weight. These compounds are obtained from the above-described esters of polyols and/or preferably polyether polyols and 4,4'-diphenylmethanediisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethanediisocyanate, 2,4 - and/or 2,6-toluylene diisocyanate or crude-MDI. In addition, you can also use liquid polyisocyanates containing carbodiimide groups, respectively, having an NCO content of from 36,6 to 15, preferably from 31 to 21 wt.%, relative to the total weight, for example, based on 4,4'-, 2,4'-and/or 2,2'-diphenylmethanediisocyanate and/or 2,4 - and/or 2,6-toluylene diisocyanate. The modified polyisocyanates can be mixed with one another or with unmodified organic polyisocyanates such as, for example, 2,4'-, 4,4'-diphenylmethanediisocyanate, crude-MDI, 2,4 - or 2,6-toluylenediisocyanate. As modified isocyanates are preferably used aliphatic and/or cycloaliphatic diisocyanates, which is modified, biuret and/or urethane groups, such as those already mentioned, are biuret and/or cyanurate groups in accordance with known techniques and who will win, at least one, preferably at least two and more preferably at least three free isocyanate groups, respectively. The trimerization of isocyanates to obtain isocyanates with which groups can be carried out at ordinary temperatures in the presence of known catalysts, such as phosphines and/or phosphorinane derivatives, amines, alkali metal salts, metal compounds and/or Mannich bases. In addition, the trimers of isocyanates which contain groups are also on sale. Isocyanates having biuret groups, can also be obtained according to known methods, for example by reacting the above-mentioned diisocyanates with water or diamines, where as an intermediate product using a derivative of urea. Isocyanates containing biuret groups, are also on sale.

The reaction according to stage (3) is conducted under conditions known to the person skilled in the art. Suitable reaction conditions are described, for example, Becker, Braun "Polyurethanes", Kunststoffhandbuch, volume 7, ed. Carl Hanser, München, 3rd ed., 1993, p.139-193.

Not necessarily in the reaction in stage (3) in the future as additives can be added low molecular weight compounds. Such compounds can be chain extenders or inhibitors. In castnet is, suitable for these purposes are, for example, primary amines having from 2 to about 20, for example, from 2 to about 12 atoms. As examples mention may be made of the following compounds:

ethylamine, n-Propylamine, ISO-Propylamine, n-Propylamine, sec-Propylamine, tert-butylamine, 1-aminoisobutyric, substituted amines having from 2 to about 20 C-atoms, such as 2-(N,N-dimethylamino)-1-aminoethane, aminomercaptan, such as 1-amino-2-mercaptoethane, diamines, aliphatic aminoalcohols having from 2 to about 20, preferably from 2 to about 12 C-atoms, such as ethanolamine, 1-amino-3,3-dimethylpentan-5-ol, 2-aminohexyl-2',2"-diethanolamine, 1-amino-2,5-dimethylcyclohexane-4-ol, 2-aminopropanol, 2-aminobutanol, 3-aminopropanol, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 5-aminopentyl, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 1-amino-1-cyclopentanemethanol, 2-amino-2-ethyl-1,3-propandiol, aromatic-aliphatic, or aromatic or aromatic-cycloaliphatic aminoalcohols having from 6 to about 20 C-atoms, where the aromatic structures are heterocyclic ring system, or preferably sollicita ring system such as naphthalene or especially derivatives of benzene, such as 2-aminobenzoyl alcohol, 3-(hydrokinetic)aniline, 2-amino-3-phenyl-1-propanol, 2-amino-1-phenylethanol, 2-phenylglycinol is or 2-amino-1-phenyl-1,3-propandiol, and a mixture of two or more such compounds.

The reaction according to stage (3) can optionally be carried out in the presence of a catalyst. Compounds that are used as catalysts, can be in principle all compounds which strongly accelerate the interaction of isocyanates with compounds which are reactive toward isocyanates, and is primarily used, the total content of the catalyst is from 0.001 to 15 wt.%, especially 0.05 to 6 wt.%, the total weight of the compounds which are reactive toward isocyanates. As examples mention may be made of the following compounds, which can be used as catalysts:

tertiary amines, such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethane, dimethylcyclohexylamine, N,N,N',N'-tetrametric-iminodiethylamine simple ether, bis(dimethylaminopropyl)urea, N-methyl - and N-ethylmorpholine, N-cyclohexylaniline, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutylamine, N,N,N',N'-tetramethylhexadecane-1,6, pentamethyldiethylenetriamine, dimethylpiperazine, N-dimethylaminopyridine, 1,8-diazabicyclo(5.4.0)undecene-7,1,2-dimethylimidazole, 1-azabicyclo-(2.2.0)octane, 1,4-diazabicyclo(2.2.2)octane (DABCO), alkanolamine, such as triethanolamine, triisopropanolamine, N-methyl - N is N-ethyldiethanolamine, dimethylaminoethanol, 2-(N,N-dimethylaminoethoxy)ethanol, N,N,N',N"-Tris(dialkylaminoalkyl)hexahydrotriazine, such as N,N',N"-Tris(dimethylaminopropyl)-second-hexahydrotriazine, preferably triethylenediamine, Penta-methylenedianiline and/or bis(dimethylamino)of the new ester; metal salts, for example, inorganic and/or organic compounds of Fe, Pb, Zn and/or Sn, in the usual oxidation state of the metal, respectively, such as chloride of Fe(II), chloride Zn, octout Pb, and preferably compounds of Sn, such as compounds of Sn(II), especially diktat Sn, diethylhexylphthalate Sn and/or compounds of Sn(IV), such as dialkyl-Sn-di(isooctylmercaptoacetate), dialkyl-Sn-di(2-ethylhexylamine), dialkyl-Sn-di(2-ethylhexylphthalate), dialkyl-Sn-di(isooctyl-mercaptoacetate), dialkyl-Sn-dilaurate, dialkyl-Sn-demolet, dialkyl-Sn-di(mercaptoacetate). In addition, as catalysts can be used amidine, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidin, of tetraalkylammonium hydroxides, such as a hydroxide of Tetramethylammonium, hydroxides of alkali metals such as sodium hydroxide, and alkali metal alcoholate such as sodium methylate and isopropyl potassium, and alkali metal salts of fatty acids with long chain having from 10 to 20 C-atoms and optionally Oh-groups as side groups. Typical lists the catalysts can be used in the AMI on its own or in a mixture, at least two of the above-mentioned catalysts.

Not necessarily as auxiliary substances and/or additives in the method according to the invention can be used with ordinary matter. Mention should be made of, for example, surfactants, agents of internal division, fillers, dyes, pigments, flame retardants, agents protect against hydrolysis, compounds having fungistaticeski and/or bacteriostatic effects, UV stabilizers and antioxidants. The pigments and/or dyes may be used in order to get tinted or colored molded product.

In General, for the reaction according to stage (3) the use of a solvent or diluent agent, as a rule, is not required. However, in the preferred variant of the embodiment mentioned reactions using solvent or a mixture of two or more solvents. Suitable solvents are, for example, hydrates, especially toluene, xylene or cyclohexane, esters, especially atilglukuronida, ethyl acetate or butyl acetate, amides, in particular dimethylformamide or N-organic, sulfoxidov, especially dimethyl sulfoxide, ethers, especially diisopropyl ether or methyl tert-butyl ether or preferably cyclic ethers, especially THF or dioxane.

In addition, the present from reenie also applies polyurethane, the resulting integrated process comprising at least the following stages,

(2) the interaction of at least one organic compound, at least one alkoxylation agent by the method described above, resulting in a gain easy polyester aliphatic alcohol;

(3) the interaction polyether aliphatic alcohol with stage (2)at least one isocyanate.

Simple polyester aliphatic alcohol, obtained according to stage (2), which is used to produce polyurethane, primarily contains at least one mixed block-ethylene oxide-propylene oxide-links or endnote propyleneoxide block or a combination of both.

In addition, the present invention relates to a method for producing polyurethane Penoplast based on polyurethane, as described in the present invention, which contains at least the following stage,

(4) foaming polyurethane used as the starting material.

The present invention also encompasses a polyurethane foam as such, obtained by foaming polyurethane obtained by the reaction according to stage (3).

The polyurethanes obtained in accordance with the present invention is mainly characterized by a low content of impurities, such as C6 connection. This makes the polyurethanes according to the invention is particularly suitable for the production of polyurethane foams, polyurethane cast films and elastomers.

Among the polyurethane foams are preferably receive polyurethane foams, which are used in the automotive and furniture industries, such as semi-rigid penalty, rigid and flexible integral foams or RLF materials (RLF-reaction injection molding).

Methods for producing polyurethane foams described in the publication Becker, Braun, "Polyurethanes", Kunststoffhandbuch, Tom, Carl Hanser, München, 3rd ed, 1993, str-265.

In a preferred variant embodiment of the present invention relates to a polyurethane produced from polyether aliphatic alcohol, obtained in accordance with stage (2), which contains at least one mixed block of ethylene oxide and propylene oxide.

The present invention also relates to polyurethane derived from a polyether aliphatic alcohol, obtained according to stage (2), which contains the end propyleneoxide block.

The polyurethane according to the present invention, especially the aforementioned polyurethane, can be suitably used to produce molded products, particularly molded products obtained from the elastic sheet PE is obraznyh source materials based on polyurethane. Particularly favorable in this respect is the low content of impurities, which is manifested in the fact that a molded product made of an elastic foam, they do not emit irritating odors.

The more narrow molecular weight distribution due to the lower content of monofunctional side connections leads to improved processing in the foaming process.

Thus, the present invention also relates to a molded product consisting of a polyurethane or polyurethane foam, respectively, obtained in an integrated manner according to the invention.

Molded products according to the invention are, for example, mattresses, pillows, molded products for the automotive industry and upholstered furniture.

You must bring the following molded articles according to the invention:

- elastic foams, in particular mattresses, moulded products for the internal parts of the car, such as car seats, sound-absorbing molded product, such as, for example, carpets and/or upholstery, sponges, pillows, bumpers, upholstered furniture, office furniture, particularly chairs, backless, orthopedic products;

- thermoplastic polyurethanes, especially for use in cables, hoses, animal stamps, supports DL the rails, films, shoes and accessories shoes, the tips of the skis and tubular bandages;

elastomers cold casting, especially for covering straps for lifting and transportation, damping elements, protectors industrial cutting tools, timing belts, screens for abrasive bulk materials, scrapers, sprockets and rollers, coating rollers, skid plates for heavy construction machines, body parts, buildings, coatings for removing burrs drums, elements, pumps and pump casing, a cover for the outer parts of the tube, a covering for the inner walls of containers, carpeting for cars, cyclones, pulleys for heavy loads, guide rollers, wheel pulleys, block pulleys, coating for conveyor tapes, coatings for pipes, coatings, resistant to hydrolysis and abrasion, covering for playgrounds truck, shock absorbers, clutch parts, coatings for buoys, linear roller skates, special rollers, shockproof elements pumps;

- integrated elastic foams, in particular steering wheel seals for air filters, the handwheel steering wheel, foam winding wires, plating containers, manual calipers, Shoe soles made of polyurethane;

- polyurethane coating, in particular floor coverings, finishing materials, that is their like a tree, leather or tin;

- polyurethane irrigation films in particular, for use as gaskets in molded products, such as the dashboard, door trim cars, seats of cars and trucks, carpeting;

- rigid polyurethane foams, in particular for use as a cushioning material or a structural material;

integral foams, in particular for use as elements of internal and external parts of structures, integrated furniture, elements of interior finish of the car, skis and snowboards, as well as the technical and functional details;

- RLF-foams, in particular, in the automotive industry for the production of precast elements used in the outer parts of vehicles, such as friction linings, wings and bumpers;

- terminally, especially for ultra-light coupling structures for use in the automotive industry, for example, for covering roofs;

- semi-rigid foams, especially for foaming elements, fixed film, skins or leather or reinforced by fibers of the structural elements.

The invention is further illustrated by the following examples, which, however, do not limit the scope of the present invention.

Examples

The piano is D.1 presents the x-ray powder diffraction pattern of the catalyst MOF-5, obtained according to Example 1 (the y-axis Y describes the intensity, and the x-axis X - scale 2-Theta).

Figure 2 presents sorption isotherm of the above-mentioned catalyst (the y-axis VA describes the amount absorbed in cm3/g STP, while the x-axis RP - relative pressure (P/PO)).

Example 1

(Getting MOF-5)
Raw materialsMolar quantityCalculatedExperiment
Terephthalic acid12.3 mmol2.04 g2.04 g
Nitrate tetrahydrate zinc36.98 mmol9.67 g9.68 g
Diethylformamide (Merck)2568.8 mmol282.2 g282.2 g

The above raw materials were dissolved in a beaker in the following order: diethylformamide, terephthalic acid and the nitride zinc. The resulting solution was made in two autoclave (250 ml), respectively having inner walls that were covered with Teflon.

Crystallization occurred at 105°within twenty hours. Then orange solvent decantation from yellow crystals, the crystals again filled in 20 ml digitiform the Ministry of foreign Affairs last again decantation. This procedure was repeated three times. Then poured into 20 ml of chloroform in a solid, which was washed and decantation mentioned solvent twice.

Crystals (14.4 g), which were still wet, was transferred to a vacuum device and dried first at room temperature in vacuum (10-4mbar), and then at 120°C.

Then the obtained product was analyzed by powder x-ray diffraction and determination of adsorption capacity of the micropores. The resulting product is characterized by x-ray diffraction pattern according to Figure 1, which corresponds to MOF-5.

Determination of sorption isotherms, as shown in figure 2, with argon (K; Micromeritics ASAP 2010) shows the isotherm of type I, typical for microporous materials, and has a specific surface area 3020 m2/g, calculated according to the Langmuir equation, and micropore volume of 0.97 ml/g at a relative pressure PP0=0,4).

Example 2 (Alkoxysilane dipropyleneglycol the propylene oxide)

Dipropyleneglycol (33.5 g, corresponds to 0.25 mol) and 0.75 g of the catalyst obtained according to Example 1 were loaded into the autoclave. After that, the autoclave was filled with 116 g of propylene oxide (2 mol). The reaction was carried out at 135°C and maximum pressure of 12.1 bar, and eventually subjected interaction 2.44 mol of propylene oxide on 1 mol is the parent substance of obtaining polyol.

Example 3 (Alkoxysilane of methyldiphenylamine ethylene oxide)

Metilpirrolidon (30 g, corresponds to 0.25 mol) and 0.59 g of the catalyst obtained in accordance with Example 1 were loaded into the autoclave. The autoclave was then filled in 88 g of ethylene oxide (2 mol). The reaction was carried out at 135°C and maximum pressure of 21.2 bar. In the end, it was subjected to interaction 2.45 mol of ethylene oxide on 1 mol of the original substance with getting polyol.

Example 4 (Alkoxysilane acrylic acid with ethylene oxide)

33.2 g of acrylic acid (stabilized 2,2',6,6'-tetramethyl-4-hydroxy-piperidine-N-oxide and phenothiazines) and 0.5 g of catalyst from Example 1 was loaded in a controlled autoclave of 300 ml in a nitrogen atmosphere. The autoclave was closed and set the nitrogen pressure of 10 bar. Then under the control of the introduced 20 g of ethylene oxide through a screw press. After five hours at a temperature of 50°the catalyst was filtered and the crude product was analyzed using gas chromatography. Based on the percent of the area was determined following composition solution (residual ethylene oxide was not taken into account):

Acrylic acid 76%, monoetilenglikolya 10%, diethylenglycol 9%, other by-products 5%.

1. How alkoxysilane organic compounds, including interaction, at least one of organic the ski connection which is able to alkoxylates at least one alkoxylation agent in the presence of a catalytic system, resulting in a gain easy polyester aliphatic alcohol, wherein the catalytic system comprises a metal-organic framework material comprising pores and at least one metal ion and at least one at least bidentate organic compound, which is connected with the said metal ion coordination bond with metal ion selected from ions of elements of groups Ia, IIa, IIIa, IVa to VIIIa and Ib to VIb of the Periodic system of elements, and bidentate organic compound is chosen among a substituted or unsubstituted aromatic polycarboxylic acids, which may contain one or more nuclei, and substituted or unsubstituted aromatic polycarboxylic acids that contain at least one heteroatom and which may have one or more nuclei.

2. The method according to claim 1, characterized in that the ORGANOMETALLIC framework material comprising pores, has a specific surface area defined by adsorption (according to DIN 66131)of more than 20 m2/year

3. The method according to claim 1 or 2, characterized in that alkoxylate agent selected from mono - or multifunctional epoxides having from 2 to 30 carbon atoms and mono - or many of the functional polyether polyols, having a molecular weight of about 600 g/mol, and mixtures of two or more of these substances.

4. The method of producing polyurethane comprising at least the following stages: the interaction of at least one organic compound, which is capable of alkoxylates at least one alkoxylation agent by means of the method according to any one of claims 1 to 3, in which a simple polyester aliphatic alcohol;

interaction polyether aliphatic alcohol, at least one isocyanate.

5. The method according to claim 4, characterized in that alkoxylation agent is propylene oxide, which is produced by the interaction of propylene with oxygen, hydrogen, and oxygen; hydrogen peroxide; organic hydroperoxide; or halohydrin; preferably by reacting propylene with hydrogen peroxide; more preferably by reacting propylene with hydrogen peroxide in the presence of a catalyst containing zeolite material; in particular, by reacting propylene with hydrogen peroxide in the presence of a catalyst containing zeolite material comprising titanium and having the structure of TS-1.



 

Same patents:

FIELD: polymer production.

SUBSTANCE: invention, in particular, relates to improved method for producing polyetherpolyols using double metal cyanide catalysts. Method is accomplished via polyaddition of alkylene oxides to initial compounds having molecular mass between 18 and 2000 and 1 to 8 hydroxyl groups containing active hydrogen atoms, reaction being effected in presence of double metal cyanide catalysts. During the polyaddition reaction, reaction mixture is at least once passed through jet disperser, in which power density is at least 105-106 J/m3 and residence time of reaction mixture per pass is at least 10-5 sec.

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FIELD: physicochemical analytical methods.

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FIELD: organic chemistry, polymers.

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29 cl, 6 dwg, 7 ex

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2 cl, 1 tbl, 23 ex

Polyether-polyols // 2263684

FIELD: polymer production.

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8 cl, 12 ex

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7 cl, 6 ex

FIELD: polymer production.

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21 cl, 2 dwg, 2 tbl, 3 ex

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5 cl, 1 tbl, 16 ex

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3 cl, 3 tbl, 6 ex

FIELD: industrial organic synthesis.

SUBSTANCE: process of producing polyether-polyols containing at most 15 ppm sodium or potassium comprises following steps: (a)interaction of initiator having at least to active hydrogen atoms with at least one alkylene oxide in presence of catalyst containing alkali metal hydroxide to form polyether-polyol reaction product; (b) neutralization of polyether-polyol reaction product obtained in step (a) by bringing it into contact with acid having pKa below 5 and water, said acid and said water being introduced in such an amounts that finally content of water is 1 wt % or of the total weight of polyether-polyol present, while molar ratio of acid to alkali metal hydroxide ranges from 0.3:1 to 1.0:1; optionally (c) reduction of content of water in reaction mixture to 0.5 wt % or less of the total weight of polyether-polyol; and (d) removal of salt crystals from polyether-polyol and recovery of neutralized polyether-polyol containing not more than 15 ppm sodium and/or potassium. In the course of neutralization, magnesium silicate or aluminum silicate is added in amount below 0.05 wt parts per 100 wt parts of polyether-polyol and also hydrated inorganic acid metal salt in amount 0.01% of the weight of polyether-polyol.

EFFECT: minimized consumption of heat during neutralization step and reduced neutralization time.

7 cl, 6 ex

Polyether-polyols // 2263684

FIELD: polymer production.

SUBSTANCE: invention relates to a method of producing polyether-polyols via catalytic addition of at least two alkylene oxides to H-functional initiators, during which operation at least one oxyalkylene unit is incorporated as a result of joint dosage of at least two alkylene oxides. Catalyst utilized is at least one metal cyanide-based compound. When performing joint dosage ratios of alkylene oxides to each other is varied.

EFFECT: enabled production of polyether-polyols without clouding and having processing-appropriate viscosity.

8 cl, 12 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to a method for preparing a water-soluble copolymer. Method involves interaction of epichlorohydrin excess with primary or secondary amine or with a mixture of primary or secondary amine and ammonia and the following addition of tertiary aliphatic amine as inhibitor of gel formation. Epichlorohydrin is dosed to primary or secondary amine aqueous solution or a mixture of primary or secondary amine with ammonia at temperature 25-40°C. Then the reaction mixture is heated to 90°C followed by dosing the additional amount of epichlorohydrin wherein the total mole ratio of epichlorohydrin to primary or secondary amine or to a mixture of primary or secondary amine with ammonia = (1.03-1.10):1, respectively. Inhibitor of gel formation is added in the amount 0.2-0.5 mole per 1 mole of epichlorohydrin excess. Invention provides preparing copolymer with structure that provides avoiding formation of gel.

EFFECT: improved preparing method.

2 cl, 1 tbl, 23 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: continuous production of polyoxyalkylene polyether product.

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

EFFECT: enhanced efficiency.

29 cl, 6 dwg, 7 ex

FIELD: organic chemistry, polymers.

SUBSTANCE: invention relates to catalysts for polymerization of cyclic esters of formula , wherein M represents tin or germanium atom L and L are independently group of formula -E14(R14)(R'14)(R''14), E15(R15)(R'15) or E16(R16); E14 represents element of 14 group; E15 represents element of 15 group; and E14 represents element of 16 group; R14, R'14, R''14, R15, R'15, and R16 are independently hydrogen atom; alkyl, cycloalkyl or aryl optionally substituted with halogen atom, alkyl cycloalkyl, aryl, nitro or cyano; rest of formula -E'14RR'R''; -E'14 represents element of 14 group; R, R', R'' are independently hydrogen atom; alkyl, cycloalkyl or aryl optionally substituted with halogen atom, alkyl cycloalkyl, aryl, nitro or cyano. Also invention relates to method for production of block- or random copolymers of cyclic esters and copolymers.

EFFECT: improved catalysts for production of heterocyclic compound copolymers.

9 cl, 6 ex

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