A method of obtaining a macrocyclic polyester
(57) Abstract:Usage: for the synthesis of macrocyclic polymers. The inventive spend cationic polymerization of substituted alpha-oxide from the group of the epichlorohydrin, nitrate pilgramage alcohol or propylene oxide in an environment of dry organic solvent and an atmosphere of dry inert gas at 0 to 20°C in the presence of a catalyst tetrahydrofuranate boron TRIFLUORIDE. 2 C. p. F.-ly, 1 table. The invention relates to polymer chemistry, in particular to methods of synthesis of macrocyclic polyethers (crown ethers).A method of obtaining macrocyclic polyethers cationic polymerization of ethylene oxide initiated by the Lewis acid. The obtained target product is a cyclic polymer of General formula
where n=3-9 
Closest to the invention to the technical essence and the achieved result is a way to obtain macrocyclic polyethers cationic polymerization of ethylene oxide in an environment of dry organic solvent, such as dioxane, benzene, methylene chloride in the atmosphere of dry inert gas at 0-20aboutWith the presence of the catalyst BF3 Get macrocyclic polyester with aranov this method ineffective, as in the solid phase polymer is practically absent. The method does not allow to obtain macrocyclic polyethers based replaced by oxiranes with the number of heteroatoms in the chain more than 11.The objective of the invention is to obtain macrocyclic polyethers based replaced by oxiranes with functional groups in the structure of the crown ether with the number of heteroatoms in the chain more than 11.To do this, hold the cationic polymerization of substituted alpha-oxide from the group of the epichlorohydrin, nitrate pilgramage alcohol or propylene oxide in an environment of dry organic solvent and an atmosphere of dry inert gas at 0-20aboutIn the presence of a catalyst of tetrahydrofuran boron TRIFLUORIDE. As a dry solvent used, the solvent basicity lower basicity of the monomer, such as methylene chloride (CH2Cl2) D=-12 cm-1or carbon tetrachloride (CCl4) D=-21 cm-1.As a dry solvent used, the solvent basicity, higher basicity of the monomer, for example dioxane (C2H8O2) D=77 cm-1.Introduction to reaction as a monomer substituted oxide allows to obtain macrocyclic polyethers of ekoobrazovanii.Use as a catalyst tetrahydrofuranate boron TRIFLUORIDE allowed to obtain macrocyclic polyethers based replaced by oxirane (target product) with a specified molecular weight distribution and to increase the yield of the target product by eliminating the influence of eye-catching in the early stages of the reaction components with high basicity and include them in the response.If used as a dry solvent, the solvent basicity lower basicity of the monomer, for example methylene chloride ( D=12 cm-1) or carbon tetrachloride ( Y=-21 cm-1), you can get a macrocyclic polyether (target product) on the basis of substituted oxiranes with the given number of heteroatoms in the chain with n=4-9 and increase the yield of the target product.If used as a dry solvent, the solvent basicity higher basicity of the monomer, for example dioxane ( D=77 cm-1), it is possible to obtain the target product with the molecular weight cycles n11 and to increase the yield of the target product.The invention is illustrated by the following examples.The reaction was carried out in a solution of dry solvent in an atmosphere of dry argon in the presence of catalysis is effected to the temperature of melting ice, the mixture of the solvent with the catalyst is added slowly (added dropwise) a monomer substituted-oxide, stirred for 5-6 hNext to water-soluble polyesters (based on propylene oxide (OP), L=48 cm-1) the reaction mixture was aged at room temperature for 10-12 h with constant stirring, followed by separation of the target product.For water-insoluble polyesters on the basis of epichlorohydrin (ECG), L= 40 cm-1and nitrate gitignore alcohol (NGS), L=55 cm-1in the reaction mixture, water was added, and the mixture was mixed for 0.5-1 h, the aqueous phase was separated from polimersoderzhashchie the organic phase, followed by the separation of the target product.The obtained products were characterized on the content of macrocycles and their molecular weight distribution by the methods of liquid chromatography at critical conditions and gel permeation chromatography.IR spectroscopic analysis of the target product confirms its purity by foreign functional groups.Examples of specific implementation method and classification of the target product are listed in the table.C-CH-CH2ONO2glycidyl nitrile
In examples 1-4 are shown obtaining the target product with low molecular weight cycles (n=4-9) with osnovnom the cm-1), ECG ( L=40 cm-1), NGS ( L=55 cm-1). The yield of the target product is 955% when the content of low-molecular-weight cycles with functional groups 70-90%
In examples 5, 7 obtained target product with high molecular cycles (n 11). The method was carried out using a solvent WITH4H8ABOUT2with basicity ( G cm-1), higher than the basicity of the monomer OP ( D=45 cm-1), ECG ( L=40 cm-1). The yield of the target product is 955% when the content of high molecular weight cycles with functional groups 70-90%
Example 6 the process was carried out on the prototype with the use of substituted oxiranes. In this case, the yield of the target product is very low (about 0.2 g) and almost no cyclic products such as low-molecular and high-molecular.In example 8 the process is carried out the method prototype obtain macrocyclic polyethers, content and yield of cyclic products, about 90%, However, these products do not contain functional groups.The above examples show that this method for the synthesis of macrocyclic polyethers universal for the class of 1,2-oxirane. In all cases, the process according to the invention, leads to brasota showed no functional groups, not contained in the structure of the monomer. Compared with the prototype of the proposed method obtained macrocyclic polyethers based replaced by oxiranes with a specified molecular weight distribution, namely the molecular cycles n=4-9 and macromolecular cycles n 11.The yield of the target product is 955% when the content of cycles with functional groups 955% that cannot be obtained by the method prototype (examples 6, 8). 1. A method of OBTAINING a MACROCYCLIC POLYESTER cationic polymerization of oxirane in an environment of dry organic solvent and an atmosphere of dry inert gas at 0, 20oIn the presence of a catalyst complex compounds of boron, characterized in that as oxirane use of substituted alpha-oxide, selected from the group comprising epichlorohydrin, nitrate pilgramage alcohol or propylene oxide, as well as complex compounds of boron tetrahydrofuranate boron TRIFLUORIDE.2. The method according to p. 1, wherein the organic solvent is used as a compound with a basicity lower basicity of substituted alpha-oxide.3. The method according to p. 1, wherein as the organic
FIELD: polymer production.
SUBSTANCE: polyoxyalkylene-polyols are obtained via direct polyoxyalkylenation of acid-sensitive low-molecular initiator with molecular weight below 400 Da in presence of double complex metal cyanide catalyst. Process comprises: (i) creation of appropriate conditions in reactor of polyoxyalkylenation in presence of double complex metal cyanide catalyst; (ii) continuously feeding into reactor alkylene oxide and above-mentioned initiator; and (iii) discharging polyether product. Loss of catalyst activity is reduced by performing at least one of the following operations: acidification of acid-sensitive low-molecular initiator before feeding it into reactor; and treatment of the same with effective amount of a substance other than acid, which reacts with base or absorbs base, before feeding it into reactor.
EFFECT: prevented catalyst from loosing its activity and essentially decreased high-molecular fraction and polydispersity of polyoxyalkylene-polyols.
21 cl, 2 dwg, 2 tbl, 3 ex
FIELD: polymerization catalysts.
SUBSTANCE: invention provides double metal cyanide catalysts for production of polyetherpolyols via polyaddition of alkylene oxides to starting compounds containing active hydrogen atoms, which catalysts contain double metal cyanide compounds, organic complex ligands, and α,β-unsaturated carboxylic acid esters other than above-mentioned ligands.
EFFECT: considerably increased catalytic activity.
6 cl, 16 ex
FIELD: organic chemistry, polymer materials.
SUBSTANCE: polyester-polyols are obtained by double metalcyanide catalyzed polyaddition of alkylenoxide to starting material containing active hydrogen atoms. Alkylenoxide is continuously fed into reactor during induction period while maintaining constant pressure in reactor.
EFFECT: method for polyester-polyol production with decreased induction time.
2 ex, 1 dwg
FIELD: polymerization catalysts.
SUBSTANCE: catalyst is composed of double metal cyanide compound, organic ligand, and two complexing components other than precedent organic ligand and selected from group including: polyethers and polyesters, glycidyl ethers, esters from carboxylic acids and polyatomic alcohols, bile acids, bile acid salts, bile acid esters, bile acid amides, and phosphorus compounds, provided that selected complexing components belong to different classes.
EFFECT: substantially increased catalytic activity.
5 cl, 1 tbl, 16 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: invention relates to improved method of preparing double metal cyanide catalysts for synthesis of polyether-polyols via polyaddition alkylene oxides to starting compounds possessing active hydrogen atoms. Method comprises following steps: (i) mixing one or several solutions of water-soluble salts of Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(VI), Cu(II), or Cr(III) with solution of water-soluble cyanide ions-containing salt or acid of Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV), or V(V) with the aid of mixing nozzle, preferably jet disperser; (ii) isolation of catalyst from resulting dispersion; (iii) washing; and (iv) drying.
EFFECT: increased catalytic activity, reduced particle size, and narrowed size distribution of particles in polyether-polyols production process.
8 cl, 5 dwg, 9 ex
FIELD: continuous production of polyoxyalkylene polyether product.
SUBSTANCE: proposed method includes introduction of first portion of mixture of double metallocyanide catalyst with initial starter into continuous-action reactor for initiating polyoxyalkynylation of initial starter after introduction of alkylene oxide. Proposed method includes: (a) continuous introduction of one or more alkylene oxides into said reactor; (a')continuous introduction of mixture of double metallocyanide catalyst with starter into inlet hole of said reactor for maintenance of catalytic activity at required level; (a")continuous introduction of one or several additional starters in addition to starter introduced into said inlet hole of reactor together with catalyst; these additional starters may be identical to said starter or may differ from it and may contain additional double metallocyanide catalyst; (b) polyoxyalkynylation of combined starters of continuous action of stages (a), (a') and (a") for obtaining polyoxyalkylene polyether product having required average molecular mass; and (c) continuous removal of said polyoxyalkylene polyether product from reactor. Proposed method makes it possible to obtain polyoxyalkylene polyether product of low degree of nonsaturation and narrow polydispersity practically containing no fractions of high molecular mass.
EFFECT: enhanced efficiency.
29 cl, 6 dwg, 7 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: invention relates to improved method for preparing double metal cyanide catalysts effective to catalyze synthesis of polyetherpolyols via polyaddition of alkylene oxides to starting compounds containing active hydrogen atoms. Method is characterized by that aqueous solutions of metal salt and metal cyanide salt are first brought to react in presence of organic complex ligands and, if necessary, one or several other complexing components to form dispersion of double metal cyanide catalyst, which is filtered to give filtration precipitates. The latter are washed with one or several aqueous or nonaqueous solution of organic complex ligands in flowing washing mode and, if necessary, one or several other complexing components, after which washed filtration precipitates are dried after optional squeezing and mechanical removal of moisture. Washing and drying stages are performed on the same filter.
EFFECT: significantly simplified process due to avoided repetitive redispersing of catalyst followed by transferring filtration precipitate to another equipment.
9 cl, 13 ex
SUBSTANCE: in phosphazene, applied on carrier, catalyst for cyclic monomer polymerisation or for substituent substitution in compound or for carrying out reaction with formation of carbon-carbon bond, carrier is insoluble in used solvent and has group, which is able to form bond with group described with general formula (1) where n is integer in interval from 1 to 8 and represents number of phosphazene cations, Zn- is anion of compound, containing atoms of active hydrogen in form obtained as result of release of n protons from compound, which contains atoms of active hydrogen, in which there are , at most, 8 atoms of active hydrogen; each of a, b, c and d represents positive integer equal 3 or less; R represents similar or different hydrocarbon groups, containing from 1 to 10 carbon atoms, and two R, located on each common nitrogen atom, can be bound with each other with formation of ring structure; R1 represents hydrogen atom or hydrocarbon group, containing from 1 to 10 carbon atoms; D represents direct bond or divalent group able to bind N with carrier. Described are phosphazene compound and phosphazene salts and methods of cyclic monomer polymerisation, substitution of substituent in compound and carrying out of reaction with formation of carbon-carbon bond using applied on carrier catalyst. According to invention method polymerisation of cyclic monomers, substitution of substituents, reactions with formation of carbon-carbon bond, etc. can be carried out with extremely high efficiency.
EFFECT: increase of efficiency of carrying out different organic reactions and absence of activity decrease even after removal and re-use of catalyst, economic benefit.
SUBSTANCE: proposed method involves interaction of, (i) at least one water soluble metallic salt, (ii) at least one water soluble metal-cyanide salt, (iii) at least one organic complexing ligand, (iv) at least one water soluble alkaline metallic salt and, not necessarily, (v) at least one functionalised polymer in conditions of precipitation, enough for the formation of a catalyst and addition of at least one water soluble alkaline metallic salt in an amount which will ensure its amount in the specified catalyst is roughly from 0.4 to 6% of the total mass of the double meta-cyanide catalyst. Also declared is the double metal-cyanide catalyst obtained using the specified method.
EFFECT: acceptable catalyst activity and the possibility of using it for obtaining polyols with the reduction in the levels of high-molecular tail fractions.
14 cl, 16 ex, 7 tbl
SUBSTANCE: invention concerns mix with activated initiation agent, which can be applied in obtaining polyalkylenepolyenes. Claimed mix with activated initiation agent includes (a) at least one initiation agent activated in advance and comprised by: (i) at least one of first initiation agents with equivalent mass of at least 70; (ii) at least one epoxide; and (iii) at least one DMC-catalyst; and (b) at least 2 mol % per quantity of initiation agent(s) activated in advance of one of second initiation agents with equivalent mass less than equivalent mass of first initiation agent.
EFFECT: elimination of necessity to synthesise expensive initiation agents with high molecular mass with catalysis facilitated by potassium hydroxide in separate assigned reactor.
7 cl, 2 ex