The method of obtaining sodium caprolactamate
(57) Abstract:Usage: caprolactamate sodium catalysts for anionic polymerization of lactams. The inventive caprolactamate sodium is obtained by metallation of the hydride of sodium caprolactam in the environment aprotic solvent at 20-80 °C and stirring for 2-5 h, using a mixed hydride of aluminium and sodium, selected from the group NaHAlH3, NaH(AlH3)2: (NaH)3AlH3. The product is separated, evaporated, and dried in vacuum. table 2. The invention relates to methods for caprolactamate sodium, used as catalyst for the anionic polymerization of lactams, for receiving polycaproamide and its copolymers.The known method (1) obtain caprolactamate sodium interaction of metallic sodium with caprolactamate at 100-120aboutWITH
Na+CLN __ NaK+0,5 H2where KL=H=0 . This method in its apparent simplicity has several disadvantages. In addition to the fire hazard of released hydrogen is partially restores the lactam to cyclohexylamine, cyclohexanol and other compounds, which generally reduce the catalytic activity caprolactamate sodium. The consequence of this is nanoproizvodstvu essence and the achieved result to the invention is a method of obtaining a (2) caprolactamate sodium interaction hydride sodium caprolactam from the reaction in organic solvents
NaH+H=0 __ NA=0+H
However, this method is not without disadvantages.Sodium hydride obtained in the USSR, the purity does not exceed 90%. A significant portion of the impurities are alkyl derivatives of sodium, which are the initiators of the occurrence of adverse reactions, with the formation of different products recovery and condensation, which reduces the catalytic activity caprolactamate sodium.The aim of the invention is a method for caprolactamate sodium.This objective is achieved in that for obtaining caprolactamate sodium use mixed sodium hydride and aluminum selected from the group NaHAlH3, NaH (AlH3)2or (NaH)3AlH3and as the solvent used diethyl ether.Source hydrides NaHAlH3, NaH (AlH3or (NaH)3AlH3get a known method (3).Chemical analysis of the obtained mixed hydrides are presented below.Found,%: Na 42,3; Al 49,5; H 7,25.NaH AlH3< / BR>Calculated,%: Na 42,5; Al 50; H 7,4.Found,%: Na 27,5; Al To 70.9; H 7,3.NaH (AlH3)2< / BR>Calculated,%: Na 27,3; Al 71,4; H 7,2.Found,%: Na 70,72; Al 25,9; H 5,85.(NaH)3AlH3< / BR>isout to get caprolactamate sodium.Their interaction with the caprolactam is carried out in an environment of diethyl ether at room temperature and stirring for reaction at a ratio of reagents:
(NAH)3AlH3+N=0=1:3 for 2-5 h, clarified water is separated from the precipitate evaporated at T-200aboutWith/HAC.The process is reflected by the equations
NAHAlH3+O __ NAO+AlH3+H2(1)
NAH(AlH3)2+O __ NAO+2AlH3+H2(2)
(NAH)3AlH3+O __ NAN-(CH2)5-CO+AlH3+3H2(3)
For example, in the synthesis according to equation (1)
to a suspension of 2 g (0,0037 mol) NaH AlH3in Et2O dispense 100 ml Et2O containing 4,2 g (0,037 mol-caprolactam).The reaction mixture is filtered off from NaHAlH3and evaporated in vacuum at 20aboutC. Received 49 g (98%) caprolactamate sodium representing a white crystalline substance, deliquescent in the open air, therefore synthesized caprolactamate sodium is stored in closed vials in an argon atmosphere.Found,%: From 52.5; H 7,3; N 10,2; Na 16,5.NAO
Calculated,%: From 52.9; H 7,4; N 10,3; Na 16,9.In table. 1 and 2 shows the results of synthesis caprolactamate sodium and it is,5%. The process is simple in execution and to use the available synthesis of source materials, to improve the quality caprolactamate sodium, i.e., its catalytic activity.One of the major advantages of the proposed method is to obtain as a by-product of aluminum hydride, which neutralizes the negative effect of H2to get caprolactamate sodium, expressed in recovery caprolactamate sodium, which leads to a decrease in its catalytic activity. In addition, the aluminum hydride is used as a reagent to obtain the source of hydrogen compounds of aluminum and sodium.Another advantage of this technique compared with the prototype and the analogue is that the production caprolactamate sodium on the proposed method makes it possible to ensure the following requirements are met:
to get the most pure and highly efficient catalyst for polymerization lactamases;
to increase the level of waste products due to the minimum defective parties polycaproamide, as a result of increased purity caprolactamate sodium, used as a catalyst for the anionic polymerization in its production - 80oWith mixing in the environment aprotic solvent for 2-5 hours, separating the clarified solution with subsequent evaporation and drying in vacuum, characterized in that the metal hydride used mixed sodium hydride and aluminum selected from the group NaH AlH3, NaH (AlH3or (NaH)3AlH3and as the solvent used diethyl ether.
FIELD: industrial organic synthesis.
SUBSTANCE: invention provides catalytic deiodination composition containing 0.95 wt parts of ethyl acetate and 8-50 wt parts of metallic zinc in the form of 3-6 mm granules. Hexafluoro-1,2,3,4-terachlorobutane production process involving use of this catalyst is characterized by that process is carried out for 20-40 h at 20-25°C, after which resulting product is washed with water at ambient temperature. Catalyst is distinguished by being accessible, inexpensive, nontoxic, and easy-to-use. Process is characterized by high yield of hexafluoro-1,2,3,4-terachlorobutane (90-98%) resulting in easiness of isolation thereof using ordinary water washing. Equipment necessities are also non-onerous.
EFFECT: increased yield of desired product and simplified technology.
2 cl, 1 tbl, 9 ex
FIELD: conversion processes of chlorohydrocarbons; catalysts for joint production of chloroform and alkane chlorides.
SUBSTANCE: proposed catalyst is just product of interaction of ferrous chloride with nitrogen-containing organic derivative - amino alcohols of common formula R2NR1OH, where R=H or alkyl C1-C2, R1=C2-C5 alkyl applied on silica gel at content of FeCl2 of 0.7-1.5 mass-% of mass of silica gel at mass ratio of FeCl2/amino alcohol 1 : (5-20). Proposed catalyst makes it possible to increase life of heterogeneous catalyst, thus excluding stage of cleaning the products of process of joint production of chloroform and alkane chlorides and decreasing the cost of process due to replacement of copper chloride by ferrous chloride in the amount lesser by at least three times.
EFFECT: enhanced efficiency.
1 tbl, 12 ex
FIELD: catalyst preparation methods.
SUBSTANCE: immobilized ionic liquid is prepared by anion-assisted immobilization of ionic liquid, for which purpose a carrier is treated with anion source, for instance with inorganic halide to produce ionic liquid or applying it onto carrier. Alternatively, ionic liquid may be immobilized because of cation covalently linked to carrier, e.g. through silyl groups, or incorporated into carrier via synthesis of carrier in presence of acceptable base. Immobilized ionic liquid are meant for use as catalysts, e.g. in Friedel-Krafts reaction.
EFFECT: optimized preparation procedures.
18 cl, 10 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to composition suitable for use in reaction zone wherein aniline is brought into contact with nitrobenzene to produce 4-aminodiphenylamine synthesis intermediates, which composition contains zeolite having internal channels with a base introduced therein to take part in above reaction. Dimensions of cross-section of channels is such that a limited reaction transition state is ensured thereby improving selectivity of reaction with regard to desired intermediates. Invention also related to the title process using above defined composition.
EFFECT: improved selectivity of 4-aminodiphenylamine intermediates production.
9 cl, 12 dwg, 7 tbl, 8 ex
FIELD: production of catalytic compositions.
SUBSTANCE: proposed method includes combining and bringing into interaction at least one component of non-precious metal of group VII and at least two components of metal of VIB group in presence of proton liquid; then composition thus obtained is separated and is dried; total amount of components of metals of group VIII and group VIB in terms of oxides is at least 50 mass-% of catalytic composition in dry mass. Molar ratio of metals of group VIB to non-precious metals of group VIII ranges from 10:1 to 1:10. Organic oxygen-containing additive is introduced before, during or after combining and bringing components into interaction; this additive contains at least one atom of carbon, one atom of hydrogen and one atom of oxygen in such amount that ratio of total amount of introduced additive to total amount of components of metals of group VIII to group VIB should be no less than 0.01. This method includes also hydraulic treatment of hydrocarbon material in presence of said catalytic composition.
EFFECT: enhanced efficiency.
29 cl, 8 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: invention relates to production of heterogeneous catalysts for processes of liquid-phase oxidation of organic compounds (phenols, surfactants) with hydrogen peroxide and can be employed for catalytic treatment of waste water to remove phenol compounds. Described is heterogeneous catalyst for oxidation of organic compounds including 90-95% polymer carrier (ion-exchange resin), 0.5-1.5% modification additive (sodium alginate or chitosan), 1-2% active component, and 3-6% cross-linking agent (glutaric aldehyde or carbodiimide), active component being horse-radish or black radish extract.
EFFECT: increased catalytic activity and reduced catalyst losses during production, storage, and use.
3 dwg, 3 ex
SUBSTANCE: catalytic composition contains the catalyst of olefin metathesis as one component, and phenol derivatives as another component, at proportion: 1 mol equivalent of catalyst to 200-1500 mol equivalents of phenol derivatives. In another modification, the catalytic composition contains as the second component the alcohol derivates which do not contain the C-H fragments at α-position to hydroxyl function, at proportion: 1 mol equivalent of catalyst to 200-1500 mol equivalents of alcohol derivatives. Another one modification of the invention has quinine or its derivatives as the second component of the catalytic composition. Particularly, the ruthenium complex with formula can be used as a catalyst of olefin metathesis.
EFFECT: number of catalyst turnover and life-time of catalyst in metathesis reaction of dialkylmaleate with ethylene are increased.
10 cl, 12 ex, 6 tbl
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: invention relates to a method of photoactivation of a photocatalyst by irradiating a composition containing the said catalyst. The method of using a photolatent catalyst (a) in which a composition containing said catalyst is irradiated before subsequent treatment is characterised by that, the photolatent catalyst is: (a1) a compound selected from a group consisting of a photolatent acid, an aromatic iodonium salt or oxime-based photolatent acid; (a2) a photolatent base compound. Also described is a substrate on which a coating made from the composition is deposited in accordance with the above described method. Also described is a method of using photolatent catalyst (a), in which a composition containing said catalyst is irradiated before subsequent treatment, characterised by that subsequent treatment is preparation of foam material and the composition contains polyol and isocyanate components and photolatent base (a2) as photolatent catalyst.
EFFECT: provision for solidification of the system.
13 cl, 10 tbl, 16 ex
FIELD: process engineering.
SUBSTANCE: invention relates to catalysis. Proposed catalyst contains alcoholate of alkaline metal in solution of monohydroxy alcohol. Note here that said monohydroxy alcohol represents isobutyl alcohol, while alcoholate of alkaline metal represents potassium isobutyl with the following ratio of components in wt %: potassium isobutyl - 10-25; isobutyl alcohol - 75-90.
EFFECT: production of biodiesel from various vegetable oils, simplified process.
18 ex, 4 tbl
FIELD: chemistry of lactams' derivatives.
SUBSTANCE: the present innovation deals with obtaining N-(2-chloroalkyl)- and N-alkyl-aromatic derivatives of lactams of the following general formula: , where R=H, Cl, R'=(CH2)3, (CH2)5 which could be modifiers of unsaturated carbon-chain caoutchoucs and rubber mixtures based upon them. The suggested method for obtaining the mentioned N-substituted lactams deals with combining N-chlorolactams and allyl benzene, moreover, as N-lactams one should apply either N-chlorobutyrolactam or N-chlorocaprolactam. The process should be carried out at molar ratio of N-chlorolactam to allyl benzene being equal to 1-1.15:1, at availability of a catalyzer as mono-tertiary-butylperoxy-α-methylmethoxyethoxyethyl ether of ethylene glycol taken at the quantity of 0.4-4.0% weight, in the medium of inert solvent, for example, chlorobenzene at 100-125° C for about 15-20 min. The innovation enables to shorten terms of reaction by 20-30 times, simplify the way for obtaining target products and widen the assortment of the obtained compounds, as well.
EFFECT: higher efficiency.
SUBSTANCE: described is a method of obtaining a catalyst of an anionic ε-capralactam polymerisation by its direct interaction with an alkali metal compound in the presence of an aprotic solvent, removed after reaction completion, with a reaction being carried out at a temperature not lower than 60°C, with hydroxides or their combinations being applied as alkali metal compounds, and as active diluents - aliphatic hydrocarbons with the number of carbon atoms in the interval 5-9 or their mixtures, which form with a reaction product - water heterogenic azeotropes, removed in the course of conversion.
EFFECT: simplification and intensification of the catalyst obtaining process, increase of the catalyst activity.
2 cl, 1 tbl, 3 ex
SUBSTANCE: invention relates to a catalyst for producing mould polyamides comprising a) at least, one lactamate, b) at least, one salt of a heteroatom-substituted organic acid selected from the group consisting of aminocaproates and/or amino-laurates of alkali and/or alkaline-earth metals and, if necessary c) lactam or a mixture of several lactams. The invention also relates to the method of producing the claimed catalyst, mould polyamide and the method of its production.
EFFECT: improving the quality of mould polyamides.
9 cl, 1 tbl, 1 ex