The method of obtaining polytetrahydrofuran or complex monoamino monocarboxylic acids with 1 to 10 carbon atoms

 

(57) Abstract:

Describes how to obtain polytetrahydrofuran or complex monoamino monocarboxylic acids with 1 to 10 carbon atoms by polymerization of tetrahydrofuran in the presence of a catalyst containing a catalytically active amount of oxygen-containing compounds of tungsten and/or molybdenum deposited on the oxide carrier, and telogen selected from the group comprising water, 1,4-butanediol, polytetrahydrofuran with a molecular weight of 200-700 Dalton, monocarboxylic acid with 1-10 carbon atoms or mixtures thereof, which consists in the fact that, as of the specified catalyst used catalyst, obtained by applying the precursors of catalytically active oxygen-containing compounds of tungsten and/or molybdenum hydroxide precursors of the oxide carriers, followed by drying and calcining at 500 to 1,000C. Technical result - high selectivity at high conversion of tetrahydrofuran. 9 C.p. f-crystals, 3 tables.

The invention relates to the production of polyoxyethyleneglycol, in particular to a method for polytetrahydrofuran or complex monoamino monocarboxylic acids with 1 to 10 carbon atoms is from polymerization of tetrahydrofuran in the presence of a catalyst, contains a catalytically active amount of oxygen-containing compounds of tungsten and/or molybdenum deposited on the oxide carrier, and telogen, which you can use monocarboxylic acid (see application EP N 0503394 F2, class C 08 G 65/20, 16.09.1992 year).

The disadvantage of this method is unsatisfactory output per unit of volume/time.

The objective of the invention is to develop ways to get polytetrahydrofuran or complex monoether with high output per unit volume/time, that is, with high selectivity at high conversion of tetrahydrofuran.

The problem is solved in the method of producing polytetrahydrofuran or complex monoamino monocarboxylic acids with 1 to 10 carbon atoms by polymerization of tetrahydrofuran in the presence of a catalyst containing a catalytically active amount of oxygen-containing compounds of tungsten and/or molybdenum deposited on the oxide carrier, and telogen selected from the group comprising water, 1,4-butanediol, polytetrahydrofuran with a molecular weight of 200-700 Dalton, monocarboxylic acid with 1-10 carbon atoms, or mixtures thereof, by as indicated kislorodsodyerzhascikh compounds of tungsten and/or molybdenum hydroxide precursors of the oxide carriers, followed by drying and calcining at a temperature of 500-1000oC. the Preferred characteristics of the proposed method, set forth in the dependent claims, the invention will be described in detail in the following.

As the oxide carriers are suitable, for example, zirconium dioxide, titanium dioxide, hafnium oxide, yttrium oxide, iron oxide (III), alumina, oxide of tin (IV), silicon dioxide, zinc oxide or mixtures of these oxides. Especially preferred are zirconium dioxide and/or titanium dioxide.

Used according to the invention catalysts generally contain 0.1 to 50 weight. %, preferably 1 to 30 wt.%, particularly preferably 5 to 20 wt.% the catalytically active, oxygen-containing compounds of molybdenum or tungsten or mixtures of these compounds, in terms of the total weight of the catalyst, and, as the exact chemical structure of the catalytically active, oxygen-containing compounds of molybdenum and/or tungsten are still unknown, and it can only be dogadat, for example, based on data from infrared spectra used according to the invention catalysts, in the basis of calculation take trioxide and molybdenum, respectively, of tungsten.

In addition to the catalytically active, oxygen-containing soedinenii molybdenum and/or tungsten PR is oradatabase sulfur and/or phosphorus, in terms of the total weight of the catalyst. As is also unknown what the chemical structure data are gray - or phosphorus-containing compounds in the finished catalyst, when calculating the content of these groups in the catalyst come from SO4accordingly PO4.

Upon receipt of the proposed catalysts in General come from the hydroxides of the respective carriers. In that case, if the data hydroxide can be purchased in trade, they can be used as starting compounds for obtaining the oxide carriers. Preferably, however, the oxide carriers use svezheosazhdennoi hydroxide, after which the deposition is usually dried at 20 - 350oC, preferably at 50 to 150oC, in particular 100 to 120oC, at atmospheric or reduced pressure.

As starting compounds for obtaining data hydroxide in General are soluble in water or hydrolysable salts forming the carrier element, for example, halides, preferably their nitrates or carboxylates, in particular, their acetates. Suitable parent compounds for the deposition of these hydroxides are, for example, chloride or nitrate Zirconia or Titania, nitrate or and the and zinc acetate. From solutions data salts precipitated the corresponding hydroxide, preferably using an aqueous solution of ammonia. Or hydroxide can be obtained by adding dilute or weak acids such as acetic acid, soluble in water, the complexes of the corresponding metals, before the deposition of the corresponding hydroxide. Another possibility is to obtain a hydroxide by hydrolysis organometallics compounds, for example, the alcoholate of the respective metals as, for example, tetradecanoate zirconium, tetraisopropyl zirconium, tetradecanoate titanium, tetraisopropyl titanium, etc.

In General, the deposition of these hydroxides is formed gel-like precipitate, which by drying receive x-ray amorphous powder. Maybe these x-ray amorphous precipitates consist in addition of hydroxides of the respective metals of the many other containing the hydroxy-group of compounds, for example, hydrates of oxides, polymer, water insoluble complexes and so on, However, as the exact chemical composition of precipitation data cannot be determined, within the framework of the present application in the name of simplicity, assume that here we are talking about the hydroxides of these metals. This is hydroxy groups precipitation, the above deposition methods.

When using silicon dioxide as the oxide carrier to obtain used according to the invention catalysts preferably take svezheosazhdennoi silicic acid, which may be obtained, for example, by acidification of a solution of liquid glass and which is better dried before processing described above for hydroxide precipitation method.

The obtained described method of forming the carrier hydroxide, respectively, silicic acid, which in this application may also be called the forerunners of the media, are the precursors of the catalytically active, oxygen-containing compounds of molybdenum and/or tungsten, preferably by impregnation of the carrier with an aqueous solution of these predecessors.

As water-soluble precursors of the catalytically active, oxygen-containing compounds of molybdenum and/or tungsten can be called, for example, water-soluble salts of tungstic acid (H2WO4) formed, for example, as a result of dissolution of tungsten trioxide in aqueous ammonia, that is, monovalent, and produced from them when acidification out(H2MoO4) formed by dissolving molybdenum trioxide in aqueous ammonia, and produced from them upon acidification isopolimolybdats, in particular, metabolite and paramolybdate. Preferably as a precursor compounds of molybdenum and/or tungsten is used ammonium salt data of tungsten and molybdenum acids by impregnation applied to serve as carriers hydroxide respectively silicic acid. About nomenclature, composition and obtain molybdates, isoprenaline, wolframates and isobologram specified in Rompps Chemie-Lexikon, 8th edition, vol. 4, pp. 2659 - 2660, publisher France Fellsburg, , Stuttgart, DE, 1985, Rompps Chemie-Lexikon, 8th edition, volume 6, page 4641 - 4644, , Stuttgart, DE, 1988, and Comprehensive Inorganic Chemistry, 1st edition, volume 3, pages 738 - 741 and 766 - 768, publisher Pergamon Press, new York, 1973 Instead of the above precursors of catalytically active compounds of molybdenum and tungsten for the application of molybdenum or tungsten on hydrocity, i.e. containing hydroxy groups predecessor media, you can also use heteroalicyclic molybdenum or tungsten, as, for example, 12-wolframtones acid (H4[Si{W12O40}]2. ropicana thus hydroxide, respectively impregnated silicic acid is dried in General at 80 - 350oC, preferably 90 to 150oC, at atmospheric or reduced pressure.

It is also possible to obtain the catalyst by careful mixing of these precursors of the catalytically active, oxygen-containing compounds of molybdenum or tungsten with one hydroxide or some hydroxides. The calcination of the precursor medium, thus provided with the relevant compounds to be used according to the invention the catalyst is carried out in the same manner as in the case of saturated compounds predecessors predecessors media. Preferably, however, used according to the invention catalysts used method of impregnation.

Soaked and dried thus, the catalyst precursor is converted into the finished catalyst by calcination in air at 500 - 1000oC, preferably 550 - 900oC, particularly preferably 600 - 800oC. During calcination of the hydroxide carriers respectively silicic acid is converted to the oxide carrier, and the ancestors of kataliticheski obrazuyutsa in these catalytically active compounds. The calcination at these high temperatures is crucial to achieve high conversion and, thus, a high output per unit volume/time when carrying out the polymerization of tetrahydrofuran. At lower temperatures, calcination of the catalysts also promote the polymerization of tetrahydrofuran, however, with low conversion. Based on infrared studies of the thus obtained catalysts Yinyan and others (see Rare Metals 11, 185, 1992) suggest that in the case supported on a carrier of catalysts based on oxides of zirconium, subsidized tungsten precursor of the catalytically active, oxygen-containing compounds of tungsten, by impregnation deposited on the zirconium hydroxide, when used high temperature calcination forms a chemical compound with the hydroxy groups of the precursor of the carrier, forming a catalytically active, oxygen-containing compound of tungsten, with respect to chemical structure and chemical activity, in particular, with regard to catalytic properties, clearly differs from the oxygen-containing compounds of tungsten, only adsorbirovannykh to serving as a carrier Zirconia. I believe that the same Sainio.

As it was stated above, when implementing the proposed method can preferably be used supported on a carrier catalysts, in addition to molybdenum and/or tungsten additionally comprising compounds containing sulfur or phosphorus, or sulfur, and phosphorus. These catalysts are obtained by a method similar to the method described above in connection with the catalysts containing only compounds of molybdenum and/or tungsten, and serving as a carrier hydroxide obtained by a similar method, respectively silicic acid, by impregnation in addition put compounds containing sulfur and/or phosphorus. Application of sulfur or phosphorus in the media can make or simultaneously with the application of the compounds of molybdenum and/or tungsten, or after it. Suitable compounds containing sulfur and/or phosphorus, obtained by impregnation of employees as carriers hydroxide respectively silicic acid in an aqueous solution of compounds containing sulfate and phosphate groups, for example, sulfuric acid or phosphoric acid. In addition, it is preferable to use for the impregnation solutions of water-soluble sulfates or phosphates, and particularly preferred is sestonic media simultaneously with the connection, containing molybdenum or tungsten, is to provide employees as a predecessor of media hydroxide phosphorus-containing heteropolyacids, and use the method described above. As examples of such heteropolyacids can be called 12-wolframalpha.com acid (H3[P{ W12O4O} xH2O) and 12-molybdophosphoric acid (H7(P{Mo2O}O628H2O). For this purpose you can also use heteroalicyclic molybdenum or tungsten with organic acids of phosphorus, for example, phosphonic acids. These heteroalicyclic can also be used in the form of salts, preferably ammonium salts.

By calcining at temperatures above heteroalicyclic to decompose catalytically active, oxygen-containing compounds of molybdenum or tungsten.

Used according to the invention catalysts partly known, and obtaining them are described in application JP N 288339/1989 and N 293375/1993, J. Chem. Soc. Chem. Commun. 1259 (1988), and in Rare Metals 11, 185 (1992). Still the catalysts are used only in petrochemical processes, for example, alkylation, isomerization and cracking of hydrocarbons, that is, in ways, not such offer is EP, in the case of the proposed method using a suspension, or advisable, in the form of molded articles, for example, in the form of cylinders, balls, rings, spirals or gravel, in particular, in the case of using a solid catalyst layer, which is preferred, for example, when using a equipped with a recirculation line reactor, or a continuous process.

As a telogen to get polytetrahydrofuran complex monoamino monocarboxylic acids in General are monocarboxylic acids with 1 to 10 carbon atoms, preferably from 1 to 8 carbon atoms, particularly preferably formic acid, acetic acid, propionic acid, 2-ethylhexanoate acid, acrylic acid and methacrylic acid.

Especially surprising and particularly advantageous is the fact that when using water and/or 1,4-butanediol as Tulegenov polytetrahydrofuran can be obtained according to the invention at one stage, with greater output per unit of volume/time. If necessary, low-molecular polytetrahydrofuran with open chain having a molecular weight of 200 to 700 Dalton, as telogen can recirculate,4-butanediol and low molecular weight polytetrahydrofuran have two hydroxyl groups, they are built not only as telogen at the ends of the chain polytetrahydrofuran, and as a monomer in the chain polytetrahydrofuran.

It is advisable telogen is fed to the polymerization in solution in tetrahydrofuran. As telogen leads to the termination of the polymerization, by choosing the appropriate number of telogen is possible to control the average molecular weight of polytetrahydrofuran or polytetrahydrofuran in the form of complex diapir. The more content telogen in the reaction mixture, the lower the average molecular weight of polytetrahydrofuran or its corresponding derivative. Depending on the content of the telogen in the reaction mixture to polymerization by using the proposed method can purposefully get polytetrahydrofuran or its derivatives with an average molecular weight between 250 and 10000. Preferably using the proposed method are polytetrahydrofuran, respectively its derivatives with an average molecular weight of 500 to 10,000 daltons, particularly preferably 650 to 3000 daltons. For this telogen add in the amount of 0.04 to 17 mol-%, preferably 0.2 to 8 mol-%, particularly preferably 0.4 to 4 mol-% in terms of tetrahydrofuran.

To prevent the formation of peroxides esters polymerization carried out preferably in an atmosphere of inert gas such as nitrogen, hydrogen, carbon dioxide or a noble gas, preferably is nitrogen.

The proposed method can be carried out periodically or continuously, and for reasons of economy usually prefer continuous exercise.

When the periodic implementation of the proposed method the reagents, i.e., tetrahydrofuran, corresponding telogen and a catalyst, usually put together in the above temperature equipped with a stirrer boiler or equipped with a recirculation line reactor to achieve the desired conversion of tetrahydrofuran. Depending on the amount of catalyst, the reaction time may be 0.5 to 40 hours, preferably 1 to 30 hours, the Catalyst is added to the stage polymerization is usually in the amount of 1 to 90%, preferably 4 to 70%, particularly preferably 8 to 60% by weight used tetrahed the t from suspended therein catalyst, preferably by filtration, desantirovaniya or centrifugation.

Freed from the catalyst, the polymerization product is usually subjected to distillation, whereby in the first stage it is advisable to separate neproreagirovavshimi tetrahydrofuran. In the second stage of purification if desired, by distillation under reduced pressure to separate low-molecular polytetrahydrofuran from the final polymerization product. Or volatile oligomers of tetrahydrofuran can be depolymerizing, for example, by means described in the application DE N 3042960 way, then recycle to the reaction.

Examples

Obtaining catalysts:

The catalyst And is obtained by adding 2600 g of zirconium hydroxide to a solution of 640 g of tungstic acid (H2WO4to 3470 g of 25% ammonia solution. The resulting mixture was stirred for 30 min, then dried at 120oC for 2 h Pass through a sieve, the resulting powder was pressed into pills the size of 3 x 3 mm, which is subjected to calcination at 450oC for 2 h tungsten Content in the resulting catalyst is 20% of its total weight, calculated as the trioxide of tungsten.

Catalysts B and C similarly, you get what is at 700oC.

Catalyst G obtained by adding 1600 g of zirconium hydroxide to a solution of 425 g of tungstic acid and 200 g of ammonium sulfate in 3470 g of 25% ammonia solution. The resulting mixture was stirred for 30 minutes, then dried at 120oC for 2 h Pass through a sieve, the resulting powder was pressed into tablets, which are subjected to calcination at 600oC for 2 h tungsten Content in the resulting catalyst is 18% of its total weight, calculated as the trioxide of tungsten and its sulfur content is 7% of the total weight of the catalyst, calculated as SO4.

Catalyst D obtained by adding 2600 g of zirconium hydroxide to 2260 g of 26.5 wt.%-aqueous solution of molybdenum trioxide in 12% aqueous ammonia. The resulting mixture is stirred for half an hour, then dried at 120oC for 16 hours To dried mass is added 40 g of 75% phosphoric acid and 1.4 l of water and stirred for 30 min, and then dried at 120oC for 2 h Pass through a sieve, and the resulting powder was pressed into tablets, which are subjected to calcination at 600oC for 2 h the resulting catalyst has a content of molybdenum, calculated as trioxide, molybdenum, T total weight of the catalyst.

Catalyst E get similar to catalyst A, except that the calcining is carried out at 675oC.

Catalyst G obtained by adding 75 g of titanium dioxide (P25, the product of the firm Degussa) to a solution of 20 g of tungstic acid (H2WO4in 100 g of a 32% aqueous ammonia solution. The resulting mixture was stirred for 2 h, then dried at 120oC for 12 h Milled to a powder which is subjected to calcination at 620oC for 2 h Obtained powder catalyst has a content of tungsten, calculated as the trioxide of tungsten constituting 20% of the total weight of the catalyst.

To obtain catalyst 3 solution 16,58 kg TiOCl2in 43,5 l of distilled water combine with 45 kg of 10% aqueous solution of ammonia by the fact that both solution at 50oC while stirring and unchanging pH 6.5 for 1 h and added to 30 l of distilled water. Then additionally stirred for one hour. The formed precipitate was separated by filtration, washed and dried at 120oC for 24 h 2.4 lbs this precipitated titanium dioxide are added to a solution of 638 g of tungstic acid in the 3.65 kg 25% aqueous ammonia solution. The resulting mixture SUP>oC for 2 h, and then at 610oC for further 2 hours, the Content of tungsten, calculated as the trioxide of tungsten, the resulting catalyst is 18.6 percent of the total weight of the catalyst.

Periodic polymerization of tetrahydrofuran:

10 g of the catalyst, prior to use is exposed to drying at 180oC and a pressure of 0.3 mbar for 18 h to remove adsorbed water, in a glass flask with a capacity of 100 ml, equipped with a device for cooling return flow, in nitrogen atmosphere suspended in 20 g contains a cycle of tetrahydrofuran, and left to stand at 50oC for 24 h Then the reaction mixture is diluted by adding 20 g of tetrahydrofuran. The catalyst is separated by filtration and washed three times, each time using 20 g of tetrahydrofuran. The filtrates are combined condensed in a rotary evaporator at a temperature of 70oC and a pressure of 20 mbar and weighed. To determine the average molecular weight (Mnpart received polytetrahydrofuran is subjected to distillation in a pipe with ball extension at 150oC and 0.1 mbar.

Average molecular weight (Mn) thus obtained polytetrahydrofuran determined by the focus of a separate type of polymer i in the mixture of polymers, and Mimolecular weight of a single type of polymer i.

Table 1 shows the output polytetrahydrofuran with periodic polymerization in the presence of different catalysts and Tulegenov and their average molecular weight Mn.

Table 2 presents the results of periodic polymerization of tetrahydrofuran to polytetrahydrofuran in the presence of catalysts subjected to calcination at different temperatures under otherwise identical conditions.

Continuous polymerization of tetrahydrofuran

Example 9

In a reactor with a capacity of 250 ml in an argon atmosphere serves 220 ml (372 g) of the catalyst based on MoO3/ZrO2/PO43-(catalyst D), previously dried at 180oC and 0.3 mbar for 20 hours At the feed to the reactor, the catalyst is covered with tetrahydrofuran containing less than 0.01 wt.% water. For pumping the reaction mixture serves as a circulation pump. After complete filling of the reactor, pump, and lines of tetrahydrofuran, the reaction mixture at 50oC for 24 h is pumped through the stationary layer of the catalyst is no longer adding tetrahydrofuran. Then for 120 h in the installation impose containing 0.2 wt.% 1,4-butanediol dostavljaet about 60. The average yield of tetrahydrofuran for reaction time (120 h) is 48.9 per cent. The average molecular weight of Mnreceived polytetrahydrofuran according to gel permeation chromatography is 2400 daltons.

Example 10

Continue as described in example 9 continuous polymerization of tetrahydrofuran in the presence of a catalyst D with continuous addition of tetrahydrofuran in the same number, however, without recirculation of the product (i.e., the pump is turned off). Saved the rest of the reaction conditions. After stabilization of the output polytetrahydrofuran the reaction product is collected within 72 hours After evaporation of the reaction mixture as described for examples with periodic polymerization, get polytetrahydrofuran with an average molecular weight of 900 daltons (according to gel permeation chromatography) in the conversion of tetrahydrofuran (THF) component of 6.8%.

Periodic polymerization of tetrahydrofuran

Periodic polymerization in the presence of catalysts E - 3 conduct described above in example 1 or 2 method. The results of these examples are shown in the following table 3.

Continuous polymerization of tetrahydrofuran in the presence of butane-1,4-diol
2(catalyst E), previously dried at 180oC and at a pressure of 0.3 mbar for 72 hours Installation polymerization fill tetrahydrofurane containing 0.5 wt.% butane-1,4-diol. The reaction mixture at 50oC for 24 h is pumped through a fixed catalyst layer. Then in the installation continuously injected 0,166 kg of tetrahydrofuran per liter of catalyst per hour. From obtained within 72 h of the product of polymerization (3.00 kg) under reduced pressure, distilled neproreagirovavshimi tetrahydrofuran, and then the polymerization product is subjected to distillation at 150oC and 0.3 mbar. Get 290 g polytetrahydrofuran, the average molecular weight of Mnwhich according to spectrum1H-NMR is 2100 daltons. The output of 9.7%. Achieved conversion per unit volume/time component 16 g polytetrahydrofuran at 2100 l of catalyst per hour.

Example 15

Repeat example 14 with the only difference that instead of butane-1,4-diol polymerization is carried out in the presence of 2.5 wt.% of acetic acid. Get polytetrahydrofuran as monoacetate with an average molecular weight of 2300 daltons.

1. The method of obtaining polytetrahydrofuran or complex monoamino monocarboxylic kizichesky active amount of oxygen-containing compounds of tungsten and/or molybdenum, deposited on the oxide carrier, and telogen selected from the group comprising water, 1,4-butanediol, polytetrahydrofuran with a molecular weight of 200 to 700 Dalton, monocarboxylic acid with 1 to 10 carbon atoms or mixtures thereof, characterized in that, as specified catalyst using a catalyst obtained by depositing precursors of catalytically active oxygen-containing compounds of tungsten and/or molybdenum hydroxide precursors of the oxide carriers, followed by drying and calcining at 500 - 1000oC.

2. The method according to p. 1, characterized in that the use of catalyst comprising a catalytically active oxygen-containing compound of tungsten and/or molybdenum or a mixture thereof deposited on the oxide carrier from a group comprising zirconium dioxide or titanium, hafnium oxide, yttrium oxide, iron oxide, aluminum oxide, tin oxide, silicon dioxide, zinc oxide or their mixture.

3. The method according to PP.1 and 2, characterized in that the use of a catalyst obtained by depositing precursors of catalytically active oxygen-containing compounds of tungsten and/or molybdenum hydroxide precursors inert oxide carriers in presets the use of the catalyst on the carrier, containing 0.05 - 10 wt.% sulfur, calculated as sulfate, and/or 0.05 - 10 wt.% phosphorus, calculated as phosphate, calculated on the total weight of the catalyst.

5. The method according to PP.1 to 4, characterized in that the use of catalyst on the carrier, containing 0.1 - 50 wt.% molybdenum and/or tungsten, calculated as molybdenum trioxide, and accordingly, the tungsten trioxide based on the total weight of the catalyst.

6. The method according to PP. 1 to 5, characterized in that the use of catalyst comprising a deposited on the zirconium dioxide catalytically active oxygen-containing compound of tungsten or molybdenum, or their mixture.

7. The method according to p. 1, characterized in that the use of catalyst comprising a deposited on the titanium dioxide or a mixture of titanium dioxide and zirconium dioxide catalytically active oxygen-containing compound of tungsten or molybdenum, or their mixture.

8. The method according to PP.1 to 7, characterized in that as telogen use water, 1,4-butanediol, a mixture of 1,4-butanediol and water, formic acid or acetic acid.

9. The method according to PP.1 to 8, characterized in that the polymerisation using tetrahydrofuran having content telogen 0.04 to 17 mol.% in p the scientists by impregnation serving as a hydroxide precursor of the carrier svezheosazhdennoi and dried hydroxide of zirconium, titanium, hafnium, yttrium, iron, aluminium, tin or zinc or svezheosazhdennoi and dried silicic acid, or mixtures of these compounds, a solution of precursors of the catalytically active compounds of molybdenum and/or tungsten and, if necessary, sulfate and/or phosphate-containing solution, followed by drying and calcining at 500 - 1000oC.

 

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29 cl, 6 dwg, 7 ex

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14 cl, 16 ex, 7 tbl

FIELD: chemistry.

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

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