A method of obtaining a polyether-oximeter-oxy(oxo) -propyl-anhydride-succinic acid (peak)
(57) Abstract:The invention relates to the production of PEAK that can be used as hardeners polymer compositions, varnishes, waxes, thickeners, reagents for the synthesis of surfactants, ion exchange polymers, flocculants water, floating agents, and so on PEAK produced by interaction of maleic anhydride and 4-methylene-1,3-dioxolane with excess maleic anhydride is not more than 1 mol.%, with the formation of an equimolar complex, with its subsequent copolymerization in the solid phase upon cooling the reaction mixture to (-4) - (+4)°C. the Mixture was kept at this temperature, then heated above room temperature, but not above 802°C, then cooled and heated, repeating the cycle at least 1 times subject to the time relationship of the cooling to the heating time in the range from 1 to 5, with subsequent distillation of the excess maleic anhydride when heated in vacuum. The invention improves the output PEAK and to reduce the number of volatile, flammable solvents. 3 table. The invention relates to the chemistry of macromolecular compounds, namely the synthesis of new polyanhydrides with simple ether linkages in the polymer chain. Such is, emulsions, suspensions; chemical reagents for the synthesis of surfactants, Catino and/or anion-exchange polymers, flocculants water, floating agents, builders of the soil, the precipitating proteins from sera and drugs prolonged action.A method of obtaining PEAK interaction of maleic anhydride (MAG) and 4-methylene-1,3-dioxolane (IOC) with the formation of an equimolar complex with subsequent copolymerization in the solid phase at room temperature, and then the selection after dissolving the reaction mixture in anhydrous acetone and precipitation of the desired product anhydrous diethyl ether (prototype) [Bagaev, S. I. , Stenina E. N. Vysokomol. Conn. B. 1998. So 40. N 11. C. 1876-1879. Russian Academy of Sciences, Moscow].The disadvantages of this method are:
1. Non-quantitative output PEAK and the long duration of the process (prototype yield ~ 70% after 168 hours).2. Increased pozharoopastnost allocation PEAK (Modules dissolution in acetone from 1:10 to 1:20; precipitation ether from 1:20 to 1:40).It is also known that homopolymerization cyclic oxides and/or dioxolane in the solid phase - equilibrium process. Riesco falls speed homopolymerization due to the reduced rate of diffusion of monomers. To identify the main technical contradictions way copolymerization equimolar complexes MAGE IOC in the solid phase it is necessary to consider the following new, previously unknown, the experimental facts mentioned in paragraphs 1-4:
1. The formation of crystalline equimolar complex MAG IOC equilibrium process described by scheme:
< / BR>where the ratio of the rate constants of forward and reverse reactions - complexation constant KarrK= KK1/KK-1which increases with decreasing temperature and decreases with its increase. This is confirmed by the fact that thermal effect of complexation of endothermic and equal to 30.5 0.5 kcal/mol and melting point of the crystalline equimolar complexes MAGE IOC (III) is in the range of 23-28oC.2. When in the crystalline phase (III) of the active centers (thermodynamically compatible admixture!) the melting point of a new drug (III) is reduced. Themselves as active centers are formed from the product (III) complexes with charge transfer scheme:
< / BR>This process is accompanied by a very weak exothermic effect.3. The copolymerization reaction (additive recognize the improving temperature of the reaction mixture promotes the decomposition of the complexes (III) and in turn, the reduction of their concentration, which causes a reduction in the rate of copolymerization.4. Additive accession complexes (III) to the active centres (IV) is accompanied by simultaneously flowing the isomerization product (II) disclosure of the double bond and oksolinovaja cycle. This process is in the presence of catalytic amounts of proton-donor additives according to the scheme:
Therefore, isomerization (II) in the product (V) excludes balance comonomers - PEAK that radically distinguishes this process from all previously known solid-phase processes homopolymerization. In the known processes the temperature rise of the reaction mixture shifts the equilibrium towards the monomer, causing depolymerization. Disequilibrium in copolymerization (III) makes it possible for PEAK with almost quantitative yield.Therefore, the main technical contradiction method copolymerization of maleic anhydride and 4-methylene-1,3-dioxolane with high yield and short duration, in the solid phase, additive attach to each other crystalline equimolar complexes is a contradiction between the need to have a process temperature below which the temperature of the process above room temperature, providing accelerated diffusion of comonomers to the active centers of the growing chains.The objective of the invention is to increase the output, reduce the duration of the process copolymerization equimolar complexes of maleic anhydride and 4-methylene-1,3-dioxolane in the solid phase with a simultaneous reduction in the number of volatile, flammable solvents.The problem is solved in that the reaction mixture is prepared with an excess, but not more than one mole percent of maleic anhydride, when cooled below room temperature, kept at this temperature, then heated above room temperature, again cooled below room temperature, then heated above room temperature, repeating the cycle of cooling-heating at least once after the last cooling is distilled off in vacuum by heating excess maleic anhydride.The essence is illustrated as set forth in paragraphs 1-4:
1. Cooling below room temperature during the preparation of the comonomers to the mixture and mixing (dissolving) causes rapid formation of crystalline complexes MAGE IOC and the transformation of these complexes in the act is active centers contribute to the formation of the copolymer PEAK in the solid phase, when the temperature of the cooling, but the emergence of the copolymer reduces the delivery rate of the crystalline complexes in the area of growth of the polymer chain. The rate of formation of the copolymer falls are "buried alive" macromolecule. According to the invention, the reaction mass is heated above room temperature, which leads first to the melting of crystalline complexes, and eventually to their decay into comonomers, in which the rate of diffusion is higher than the rate of diffusion of crystalline complexes.Subsequent to the heating cooling below room temperature promotes the formation of crystalline complexes in the zone "buried alive" macromolecules and increase the molecular weight of the growing chains PEAK. While using crystalline complexes in the zone of the growth of polymer chains, the rate of formation of the copolymer is lowered again, and then again repeat the cycle of heating-cooling, causing the processes in the above-mentioned order.Alternating cycles, cooling - heating, gradually reduces the amount not included in the copolymer of comonomers. The best way is to carry out reaction to 94-98% output PEAK. This is achieved 2-3 cycles. After the final KLH">Since thermal effect of the formation of the crystalline complex and thermal effect their copolymerization almost equal to and opposite in sign, and the melting point of the crystalline complexes is in the range of 23-28oC when cooling is impractical to significantly reduce the temperature from the room. The most appropriate cooling to temperatures in the range from -4 to 4oC. At a lower temperature cooling deeper improve yield and reduce the duration is not observed, but rising energy costs. The upper limit of heating is limited by the boiling point of the most volatile of the co monomer and is 802oC.2. In table. 1, the comparative characteristics of methods of obtaining PEAK prototype (experiments 9 and 10) and according to the invention (experiments 1-8).As can be seen from comparing experiments 5 and 9, the output PEAK the proposed method 72% is achieved in 24 hours, while the output PEAK 70% of the prototype can only be achieved through 168 hours. Therefore, when 70% of the output of the proposed method is effective in 7 times.From a comparison of experiments 2 and 10 show that the proposed method for a 49.5 hours is achieved yield 87%, at the same time (as in the prototype) 168 hours for the proposed method achieved output PEAK from 92 to 98%, what 22-28 % more than the prototype. From the comparison of experiments 1 to 8 between the ratio of cooling time to the time of heating can be seen that for the approximation to quantitative yield better at the beginning of the process to have more time cooling time heating, and at the final stage to the contrary.In table. 2 shows the comparative performance of the methods of obtaining PEAK (experiments 11 and 12) of the proposed method and (experiments 13 and 14) of the prototype depending on the material of the reactor is a stainless steel NT and heat-resistant glass "Pyrex".As can be seen from the data table. 2, the proposed method has the regulation to the passage of heat flow by applying more heat-conductive material of the reactor. Thus there is an even sharper increase in the yield of PEAK and reducing the duration of the process, while the choice of material of the reactor is not reflected on the output PEAK and duration of the process of the prototype.In table. 3 shows the dependence of output PEAK on the number of redundantly entered maleic anhydride.As can be seen from the data table. 3, the proposed method is most effectively realized when small, not more than 1.0% ASS="ptx2">Almost quantitative yield is achieved for 5 hours, while the prototype to ensure a practically quantitative yield of the process copolymerization equimolar complexes MAGE IOC should be not less than 30 days.Introduction in the reaction mixture an excess of the MAGICIAN simplifies the operation of allocating PEAK vacuum when heated, because stands out only one clean comonomer (the MAGICIAN ) is suitable for reuse. In addition, if the excess in the reaction mixture of 4-methylene-1,3-dioxolane reduced output PEAK due to the parallel running of homopolymerization 4-methylene-1,3-dioxolane under the same reaction centers cationic type.3. Examples of carrying out copolymerization of maleic anhydride (MAG) and 4-methylene-1,3-dioxolane (IOC).Experience 1. The MAGICIAN used a skill h and/or h D. A., but be sure before applying sublimated in vacuum at a residual pressure of 20 mm RT. Art. and temperature 52-55oC. the IOC after cleaning had characteristics that were specified in the prototype. A portion of the MAGICIAN was placed in a glass reactor, equipped with two cameras. One of them was loaded crystal MAGE, and in another liquid IOC. After cooling to a temperature of 4
Found, %: C 43,83; 43,51; H 5,96; 5,35.For C8H10O8H2O calculated, %: C 43,64; H the 5.45.Received PEAK in the form of a monohydrate used:
4.1. To precipitate proteins from cheese whey.Industrial tests were carried out at the Kirov dairy plant. In accordance with the test report from 30.03.99, testing the acid whey obtained on the cheese line A-OPT with a pH of 2.5 to 4.5, on the precipitation of proteins of 0.2% aqueous solution PEAK technologically efficient. No additional hardware for 10 minutes is deposited to 50 kg protein mass is in 1 tonne serum. Protein mass after centrifugation at one hundred the STI 18% increase to cottage cheese. Content PEAK serum was 0,004-0,001%.4.2. To obtain the average sodium salt PEAK neutralization with a calculated amount of an aqueous solution of NaOH, and the average salt PEAK in the aqueous solution used in the production of cigarette paper. It was shown that the average salt PEAK with a concentration of 0.0004% improves quality cigarette paper by 5-10% for all indicators. The company "elikon" produced 5 tons of cigarette paper of high quality, it is shown that very high manufacturability using the average salt PEAK to stabilize the deposition of the chalk - filler, cigarette paper.An important advantage of the proposed method to obtain PEAK is practically quantitative yield with very acceptable duration of the process, which on average 30-50 times lower than the duration of the prototype. This is achieved by cyclic temperature cooling-heating below room temperature and above room temperature. In conditions of mass production (and the unique properties of PEAK provide the necessity of its organization), each of 0.1%, or even 0.01% of output is crucial.The second advantage of the proposed method is the scarfing high fire process of obtaining PEAK.The third important advantage of the proposed method is used for copolymerization equimolar complexes MAGE IOC excess MAGE no more than 1% molar, which ensures a high concentration copolymerizate complexes (high speed process), the exclusion of incidental process homopolymerization 4-methylene-1,3-dioxolane and receiving at the end of the process, pure Mage, suitable for reuse. The latter says that if a continuous process even when receiving almost quantitative yield PEAK overdose to 1% molar of the Magician applies only to the initial loading of the reactor and in the future it return the product.In addition, mass production of PEAK will allow you to organize production precipitator albumin protein from milk, cheese and/or cheese whey, which is equivalent to the increase in protein mass is equivalent proteins of chicken eggs in volume to 200 million per each region of Russia.A very promising direction of use PEAK for the production of coated paper, high-strength papers, hardeners composite materials and as a highly active macromolecular reagent with various vedesu drug, modifying, protective, water-holding and other drugs. A method of obtaining a polyether-oximeter--hydroxy(oxo)-propyl-anhydride-succinic acid by the interaction of maleic anhydride and 4-methylene-1,3-dioxolane with the formation of an equimolar complex with subsequent copolymerization in the solid phase, characterized in that maleic anhydride is used in excess, but not more than 1 mol.% in relation to the equimolar ratio, and the copolymerization process is carried out at cooling the reaction mixture to (-4) - (+4)oC, kept at this temperature, then heated above room temperature, but not above 80 2oC, then cooled and warmed in the modes described above, by repeating the cycle of cooling - heating at least once and keeping the ratio of cooling time to time of heating in the range from 1 to 5, with subsequent distillation after the last cooling excess of maleic anhydride, by heating in vacuum.
FIELD: polymers, immunology.
SUBSTANCE: invention relates to polyanionic norbornan derivatives of formula I: , wherein or is residue of another oxygen-containing monomer, such as ; n>=15. Preferably n = 35-100 (polymerization ratio); M is H, Na, K, NH4; X is OH, OM, ONH3-Y-Nb, NH-Y-Nb, wherein not less 3 % of total X represent sum of ONH3-Y-Nb and NH-Y-Nb (modification ratio with norbornan), and spacer group -Y- represents - (Yi)m [Yi is CH , CH(CH3), CH(CH2CH3); m>=0, preferably m = 1-3). And norbornan pharmacophor has formula , wherein represents bicyclic norbornan carbon skeleton including seven carbon (C) atoms in 1-7 sites and one (any) substituent from R1, R2a, R2b, R3a, R3b, R4, R5a, R5b, R6a, R6b, R7a, R7b, represents covalent bond between Nb and Y; and the rest eleven substiruents represent H or alkyl, or two by two represent covalent chemical bond in bicyclic hydrocarbon skeleton, i.e. additional double bond between carbon atoms. Method for production of formula I compounds also is disclosed. Said compounds have high selectivity index in relation to HIV-1 strains, having resistance to known azidotimidine pharmaceutical agent.
EFFECT: polyanionic norbornan derivatives useful as active ingredients of antiviral pharmaceutical formulation.
3 cl, 6 ex, 2 tbl, 4 dwg
FIELD: chemistry of polymers, chemical technology.
SUBSTANCE: invention relates to a bicomponent polymerazible composition consisting of two components. The first component includes complex of organoborane and amine comprising trialkylborane and one or some compounds comprising at least one heterocyclic fragment with an opening cycle. The second component includes Lewis acid able to initiate polymerization of compounds comprising heterocyclic functionality with opening cycle. These compounds are able to take part in free-radical polymerization wherein heterocyclic fragment with opening ring represents a substituted three-membered ring with oxygen atom as a heteroatom. Also, invention relates to a method for polymerization of abovementioned composition, to method for gluing two or more substrates each with other, to method for modifying a polymer surface of low surface energy, to method for applying cover on substrate using the claimed composition, and to composition for applying a cover comprising abovementioned composition, and to laminate. Invention provides preparing adhesive compositions able providing adhesion to substrates of low surface energy and to glue their to other substrates without carrying out the vast preliminary treatment. The composition possesses improved stability, strength and adhesion at increased temperatures.
EFFECT: improved and valuable properties of compositions.
11 cl, 15 tbl, 81 ex
SUBSTANCE: present invention relates to polyhydroxyethers used as film materials and protective coatings with improved operational characteristics. Polyhydroxyether is a compound of formula: n=70-180.
EFFECT: said polyhydroxyethers have improved fire-resistance, adhesion, strength and thermal characteristics, resistance to water and alkaline aggressive media, as well as film-forming properties and good solubility in polar solvents.
SUBSTANCE: claimed invention relates to copolyhydroxyesters based on bisphenol A and tripticene diole-2,5, which can be used as film materials with improved heat resistance. Said copolyhydroxyesters represent compounds of formula: , where n=30-100, m= 100-30.
EFFECT: obtained copolyhydroxyesters of said structure possess improved heat resistance, good solubility in polar solvents and film-forming properties.
1 tbl, 3 ex
SUBSTANCE: claimed invention relates to tripticendiole-2,5-based polyhydroxyesters, which can be used as heat-resistant coatings. Said polyhydroxyesters represent compounds of formula: , where n=60-180.
EFFECT: obtained polyhydroxyesters of said structure possess improved heat-resistance, are capable of forming coatings and are well-soluble in polar solvents.
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