The method of obtaining full ethers of oligomers of 1,2 - oxirane
(57) Abstract:The invention relates to methods of producing polyether of polyglycols (oligomers of 1,2-oxirane) and can be used in chemical industry for production of surfactants, plasticizers, binders, complexing agents, and so on, Get full ethers of oligomers of 1,2-oxirane by oxyalkylene complex alkoxyalkane with Lewis acid olefin oxide, and as alkoxyalkane use of dimethyl or diethyl ether at a molar ratio of ether and a Lewis acid is 1:0,03-0,05, the feed rate of the olefin oxide support in the range of 0.0004-0.0005-M/min, and the reaction is carried out at 10-30oC. technical result Achieved - simplifying the process, reducing energy and material costs. The invention relates to the field of chemistry polyethers, in particular a process for the production of polyethers of polyglycols (oligomers of 1,2-oxirane), and can be used in chemical industry for production of surfactants, plasticizers, binders, complexing agents, etc.There are many ways of practicalapplication (patent Germany 1129147, 1962), the interaction of mono - or polyethers with oxacillin in the presence of Lewis acid (patent GB 1574485, 1980).These methods complete polyesters are either multi-stage, because first get diols or bifunctional derivatives, which are then alkylate, or, as in the latter case, to obtain oligomers higher homologous series (with a degree of polymerization of >4) repeated reaction with the obtained low molecular weight full esters.The most common is the method of obtaining full ethers of glycols and polyglycols by oxyalkylene alcohols oxides of olefins in the presence of acid catalysts such as Lewis acids. According to this method first retrieves cellosolve, and when excess alcohol is full esters of glycols (O. N. Diment, K. S. Kazan, A. M. Miroshnikov "Glycols and other derivatives of oxides of ethylene and propylene" -M.: Chemistry, 1976, pp. 306-316). The disadvantage of this method of production is their low yield (20%), because the main product is monoether - cellosolve.Closest to the proposed method according to the technical essence is a way of dimethyl esters of oligomers of 1,2-Okie esters of oligomers of 1,2-oxirane formed in one stage by oxyalkylene complex 1,2-dimethoxyethane with Lewis acid oxide olefin at a certain ratio of the components of the reaction system.An important achievement of the prototype method is the ability to complete simple esters of oligomers of 1,2-oxirane including the degree of polymerization of >4 at one stage.The disadvantages of the prototype method can include the inability to use, in this case, widely available tonnage of chemical reagents (e.g., methyl and ethyl esters) due to the high stability of its complex with the Lewis acid. In addition, used in the method-prototype 1,2-dimethoxyethan has a higher boiling point, which complicates the process and increases energy consumption at the stage of selection of the target product.Object of the present invention is to provide a highly efficient one-step method of obtaining full ethers of 1,2-oxirane with a degree of polymerization greater than 4, allowing the use of widely available tonnage dimethyl (diethyl) ether and reduce energy and material costs.The solution of this problem is achieved by the proposed method, complete the simple esters of oligomers of 1,2-oxirane by oxyalkylene complex alkoxyalkane with Lewis acid oxide olefin, in which Cuica, equal to 1:0.03 to 0.05, the feed rate of the olefin oxide support in the range of 0.0004-0.0005-M/min, and the reaction is carried out at 10-30oC.From literature it is known that the Lewis acid forms with methyl and ethyl esters of a stable complex. For example, apirat boron TRIFLUORIDE is a common catalyst in the ionic polymerization of olefin oxides, which process is running at the active centre of zwitter-ionic nature of obtaining cyclic products (R. I. Kern, J. Organ. Chem. 1968. V. 33. P. 388-390).Adding to the equimolar ratio of the ether-the Lewis acid is equal to the amount of olefin oxide is formed oxonium salt of the appropriate acid Lewis (H. Meerwein, E. Battenberg, H. Gold, J. fur Prakrische Chem. 1940. V. 154. P. 83). For example, in the case BF3and diethyl ether is formed Et3OBF4at which the polymerization of olefin oxides also occurs with formation of a cyclic product. The formation of low molecular weight linear products, the degree of polymerization not exceeding four in excess of these esters is possible (at a molar ratio of the ether-oxide olefin of 2-5:1, patent GB 1574485, 1980). Products of higher molecular mass in these conditions cannot be obtained.Conducted and what Luisa able to dissociate on essential due to the formation of carbocation (detected by NMR spectroscopy), under certain conditions, can become an active centre for the disclosure of the cycle of olefin oxide and growth of the linear chain to degrees of polymerization of the big 4. Further studies showed that the complex of the Lewis acid with diethyl (dimethyl) ester can also dissociate with the formation of carbocation (detected by NMR). However, when you add in the oxide olefin she takes the Lewis acid itself with the formation of active centers zwicker-ionic nature, and the reaction quickly "falls" towards the production of cyclic products. To suppress competing processes and shift the reaction towards the formation of linear products, it is necessary to conduct the reaction so that the feeding speed of the olefin oxide is equal to the speed of its entry into the linear polymer. In this case, it becomes impossible to process with the formation of the active center zwicker-ionic nature.As a result of experiments, it was found that this condition is confirmed by the lack of reaction products of cyclic oligomers) molar ratio of dimethyl (diethyl) ether and a Lewis acid is 1:0,03 - 0,05, and maintaining the feed rate ocisoC.Examples of the method.Example 1. In a flask with stirrer, filled with argon, loaded 0.74 g (0.01 M) of diethyl ether and 0.07 g (0,0005 M) BF3THF (tetrahydrofuran). Under stirring at 20oWith added dropwise 12 g of epichlorohydrin (ECG) at a rate of 0.0004 M/min for 4 hours At this temperature the reaction mixture should not exceed 30oC. Then stirring continued for a further 2 hours After 6 hours, the product yield 10.5 g (80 %). Catalyst - BF3neutralized Cao (2 g) under stirring for 30 min, then filtered. Next, unreacted ECG Argonauts under slight vacuum. The reaction product is a viscous colorless or light yellow substance with a degree of polymerization ~ 30 MM (about 3000), end C2H5-O-groups. By IR - and NMR-spectroscopy shows the absence of the polymer hydroxyl groups. Quantity (availability) of cyclic products cannot be determined by liquid chromatography.Example 2. 1.2 g (0,26 M) dimethyl ether and 0.07 g (0,0005 M) BF3THF is added 15 g of epichlorohydrin for 4 hours at a temperature of 20+10oWith speeds of 0.0004 M/min. and the product Yield of 14.2, the Procedure selected isExample 3. To a mixture of 0.7 g (0.02 M) of dimethyl ether and 0.13 g (0,0005 M) SnCl4added 12 g of epichlorohydrin for 4 hours at a temperature of 15+10oWith speeds of 0.0005 M/min. and the product Yield of 9.5, Neutralization of the catalyst was carried out by the water - to 10-fold excess and its subsequent filtering. Procedures for the isolation and analysis of polymer similar to example 1. The reaction product is a linear oligomer with MM about 1500 (n ~ 15).Example 4. To a mixture of 0.95 g (0,0012 M) diethyl ether and 0.1 g (of 0.0004 M) SnCl4added 10 g of epichlorohydrin for 3.5 hours at a temperature of 20+10oWith speeds of 0.0005 M/min. and the product Yield of 9.1, the Procedure of washing the catalyst is similar to example 3, and the isolation and analysis of polymer example 1. The reaction product is a linear polymer with MM about 1500 (n ~ 15).Example 5. To a mixture of 0.74 g (0.01 M) of diethyl ether and 0.07 g (0,0005 M) BF3THF at 20oWith added dropwise 10 g of propylene oxide with a speed of 0.0004 M/min. and the product Yield of 8.8, Procedures for the isolation and analysis of polymer similar to example 1. The reaction product is a linear oligomer with about 1200 MM (n ~ 20).Example 6. To a mixture of 0.75 g (0.01 M) of diethyl ether and 0.07 g (0,0005 M) BF3THF at 10oWith added dropwise 10 g of oxide is 1. The reaction product is a linear oligomer with about 1000 MM (n ~ 30). The method of obtaining full ethers of oligomers of 1,2-oxirane by oxyalkylene complex alkoxyalkane with Lewis acid oxide olefin, characterized in that as alkoxyalkane use of dimethyl or diethyl ether at a molar ratio of ether and a Lewis acid is 1: 0.03 to 0.05, the feed rate of the olefin oxide support in the range of 0.0004-0.0005-M/min, and the reaction is carried out at 10-30oC.
FIELD: polymer production.
SUBSTANCE: polyoxyalkylene-polyols are obtained via direct polyoxyalkylenation of acid-sensitive low-molecular initiator with molecular weight below 400 Da in presence of double complex metal cyanide catalyst. Process comprises: (i) creation of appropriate conditions in reactor of polyoxyalkylenation in presence of double complex metal cyanide catalyst; (ii) continuously feeding into reactor alkylene oxide and above-mentioned initiator; and (iii) discharging polyether product. Loss of catalyst activity is reduced by performing at least one of the following operations: acidification of acid-sensitive low-molecular initiator before feeding it into reactor; and treatment of the same with effective amount of a substance other than acid, which reacts with base or absorbs base, before feeding it into reactor.
EFFECT: prevented catalyst from loosing its activity and essentially decreased high-molecular fraction and polydispersity of polyoxyalkylene-polyols.
21 cl, 2 dwg, 2 tbl, 3 ex
FIELD: polymerization catalysts.
SUBSTANCE: invention provides double metal cyanide catalysts for production of polyetherpolyols via polyaddition of alkylene oxides to starting compounds containing active hydrogen atoms, which catalysts contain double metal cyanide compounds, organic complex ligands, and α,β-unsaturated carboxylic acid esters other than above-mentioned ligands.
EFFECT: considerably increased catalytic activity.
6 cl, 16 ex
FIELD: 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: polymer production.
SUBSTANCE: polyol polyethers are prepared by cycle-cleaving polymerization of ethylene oxide and at least one alkylene oxide having at least three carbon atoms in molecule and attachable to H-functional initiator in presence of catalyst. H-functional initiator binds up to 40% (based on the weight of final polyol polyether) of ethylene oxide or mixture thereof with aforesaid alkylene oxide with at least 98 wt % ethylene oxide in presence of catalyst, which is at least one basic compound. To thus obtained polyol polyether, at least one alkylene oxide as defined above or mixture of ethylene oxide with the latter containing up to 20 wt % ethylene oxide is chemically added using as catalyst at least one metal cyanide-based compound.
EFFECT: enabled preparation of polyol polyethers with high level of ethylene oxide and low hydroxyl number.
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
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