SU707524A3 - Method of preparing non-ionogenic boranic resins - Google Patents

Description

(54) METHOD FOR OBTAINING BORANBUM EXAMPLES - RESIN

707524 Preferably, a 25% excess is used ;; (weak base in the resin. After the 7taHffK stadion windows), you can remove the Kysolota, sa-t & JtoE & oCc with a suitable drying agent with a hygienic plant, such as MfSTAHOMTMToTeMTORTM, you can use a suitable drying agent. dimethylformamide, etc. Alternatively, the resin may be dried or in vacuo, according to the preferred embodiment of this stage of the resin, the reaction is carried out in a periodic manner and a stoichiometric amount is added to enter all the protonated groups isloty. For this process, it is preferable to continue the reactions, such as at 6th 6th of the 6th, full of diffusions, c: tO S cherblek resin. The borans are preferably introduced into the protonated resin by treating the resin continuously in a column, or periodically with a bored solution of boron hydroxide, sodium, or potassium in the appropriate solution, such as methanol, ethyl, dimethylformamide, etc., at a temperature of O-ISO C, preferably with Room. alkyl, used in the present descriptions and the inventive formula, means alkyl groups with both direct and branched iHypo, which can contain up to three substituents, preferably up to 2 substituents, more readily up to the third parent, in: l5rann from the group, therefore from hydroxyl, mercaptofluoride, chlorine, bromine, iodine, nitro, yeToxy, ethoxy, isopropoxy, amino, methyl: mino, dimethylamino, ethylamino, ethylamino, dimethylamino, amino, methyla: mino, dimethylamino, ethylamino, ethylamino, dimethylamino, amyloxy and dimethylamido. The term aryl means aryl groups, for example, phenyl, naphthyl and diphenyl, which may contain up to three substituents, preferably up to two substituents, more preferably up to one substituent, selected from the group consisting of and; s fluorine, chlorine, bromine, iodine, nitro, methyl, ethyl, methoxy, ethoxy and trihalomethyl., V, The term aralkyl means aralkyl groups such as benzyl, phenethyl, phenylpropyl, butylmethyl and naphthylethyl, which are up to three substituents, preferably up to two substituents, more preferably up to one substitute selected from the group consisting of fluorine, chlorine, bromine, yoy 7 yyy 0, yyTeyl, et eyl, meto1 1, 3 current and and trig | i5f yon; Itetil; - ... "-: -.- Preferred non-ionic borane" resins according to the present invention are those for which T has the meaning of the group, ..-. .- .. ..-. . . —C — NH—, where Z is nitrogen; R and R2 Independently of each other, are hydrogen, () - unsubstituted alkyl, () - non-substituted aryl or () substituted aralkyl. l.:.:; -. . . : The most preferred non-ionic borang resins according to the present invention are those wherein T is a group,. -, .- i, ...: ...:, .... - Q:. -. ; -. -: .... II. . , .. —C — YAN—, where Z is nitrogen; . R and R 2 are different from each other to hydrogen, () is an unsubstituted alkyl or unsubstituted phenyl, diphenyl, benzyl or phenethyl. Solid non-ionic crosslinked boranes, possessing breakdown salts, and the resin according to the invention are highly selective reducing agents that are particularly useful for selective recovery at room temperature in both aqueous and non-aqueous media — mercury, silver, gold, platinum , Palladi, give birth, iridi, antimony, mice and bismuth; when etrm, the reduction of copper, nickel, zinc, iron / lead, tin, cadmium, vanadium, chromium, uranium, thorium, cobalt, tile, alcohol, and metals of groups I and II of the periodic table is excluded. Joss resins tan metal ions in solution by transferring electrons and deposition of reduced metals on and / or in resin. : Warrior resins can be applied over a wide range of pL values of 1.0 and less than 8.0. Resins are preferably used in the Ply Interval of approximately 2.0-4.0, ooran Sjols; Stable: in only acidic and basic conditions. But also in air. Another distinctive feature of the reduction process is the ability of the resins to concentrate products on the resin, thereby accomplishing the cleansing and purification of the obtained Hbix products BEFORE their hydrolysis and removal from the resin. Although macrosetch resin is preferred, it can be used as a reducing agent; but it can also use neon brans resin - a reducing agent according to the invention in the form of gels or any other particles. Recovered metals. Ca and / or non-abrasive boron resins precipitated

The reducing agents according to the present invention may be removed from the resin either by dissolving in eilbic acid or, in the case of mercury, by treating with hot water. The most preferred method of obtaining the recovered precious metal from the resin is burning the resin, since the cost of the precious metal is much higher than the cost of the resin.

These non-ionic borane resins have the advantage over ion exchange resins that when using resins, resins suspect a leak due to different ion exchange equilibria for each particular metal ion and ion exchanger. The leakage associated with the kinetics of ion-exchange equilibrium does not cause a leak when working with non-borane borane resins. These resins reduce the metals to their zero oxidized state and precipitate; they are in and / or in the resin. Another advantage of the resins, in particular, microgrid resins, is their ability to contain large quantities of reduced metals before breakthrough. ., ..:;.:.: ....

A preferred example of an embodiment of the present invention is the use of solid non-ionic crosslinked / amine o- and phosphonoborane resin-reducing agents as starting materials for the preparation of novel metallic catalysts for hydrotipation reactions. Resins containing the resulting metal may be subjected to pyrolysis to produce coal; EOH-methane: a reducing catalyst, or they can be burned in the presence of oxygen to produce a metal and: as koreols, moreover, this process produces metals or a mixture of metals ;.

Example. Synthesis of Amino Borane Resin-Based Acrylic Resin.

Stage A. Protonation. Sample

(50 g) Acrylic Macro Mesh, including a weak resin base with a weak base base of 5.4 Meq. Of a weak base per 1 g of dry resin, mixed with an aqueous solution containing 360 m: eq of hydrochloric acid

(30% excess) for 5 hours. The resin is washed with deionized water to neutral pH, then with two portions of M Acetone 300 ml each, then dried under vacuum at 50 ° C for 8 hours. Exit 59.9 g.

Stage B. Addition of boranes. In a round-bottom three-neck flask with a capacity of 500 ml, equipped with mehayich: yoyskoy stirrer with a hermetic shutter, an addition funnel with a device

To sshsensirovaniya pressure and bubbler for mineral oil, place a sample (52.8 g, - 238.1 M .. eq. I) dry acrylic macro-retina, including a weak resin base (in the form of the hydrochloride salt) containing 4.51 g / m. I equivalent to 1 g of dry. Then, a solution of sodium borohydride (10.0 g: purity 97%; 256 m eq; an excess of 7%) in 250 ml of dry H, N-dimethylformamide is added quickly with continuous stirring. The mixture is stirred at room temperature until the evolution of hydrogen gas ceases. The N, N-dimethylformamide is separated by filtration, remaining. The resin is washed on the filter with a back-flow of de-ionized water until the reaction to the chloride ion is stopped by adding silver nitrite and reaching a value of about 7. Then the resin is dried in vacuum at 30 ° C.

PRI me R 2 Synthesis of aminoborane resin-reducing agent based on

styrene / - / .:,.; -.:, ..,,

Stage A. Protonation. According to the method described in example 1, stage A, but with the use of macro-retina, including a weak resin base, on the basis of style 1, the required intermediate prothr is produced

Stage B. Addition of borane. The procedure described in Example 1, Stage B, using a protonating macro-retina, including a weak base of resin and a basis of styrene, produced the desired borane addition product. ; /; - /: -.;:. .., ..

PRI m e r 3 “Equilibrium capacity during periodic operation for various; precious metals.

the equilibrium capacity of the cell during the period of work was determined by examining the interaction of a known amount of the amboro resin with an aqueous solution of metal ions with continuous shaking for 16 hours. The base and final metal ion concentrations are determined by atomic absorption spectroscopy, and the capacitance is calculated by difference.

Aminoborane resin samples are brought into contact with aqueous solutions AiSb, Pdce | 7 and Ptce | known concentration according to the method described above .;

Example 4. Extraction of precious metal by the method of burning.

Removing the metal from metal-filled beads is easily performed by burning the resin matrix in an oxygen atmosphere. .

Claims (1)

A sample of resin filled with gold (3.004 g) is burned in a furnace for a period of 800 minutes for 30 minutes. Regenerating - brightly colored gold metallic beads (1.646 g), which corresponds to an initial weight of 55%. Kings are similar in appearance with an untreated surface. Similar results were obtained for resins filled with palladium and platinum under the same conditions. Example 5. Obtaining catalysts. Samples {1.00 g) filled with palladium or platinum are subjected to pyrolysis under nitrogen current for 30 minutes. The resulting spherical flakes resemble coal balls with a high density, which is due to the presence of metal. Example 6. Selective reduction of metals: the interaction of the amino borane resin in various metals is determined by placing the sample (O, S in the bottle and Adding a concentrated solution of the metal ion or complexion to be studied. The school is stored for three weeks to ensure sufficient contact time. The reaction is detected either by the following of the following 4 months, for example, by loss of color, weight gain of the rins washed with water and vacuum in dry water. and by their ability to further reconstitute the A & C solutions. Similarly, the recovery indicates that the ions under investigation have not reacted with the resin. Example 7. Analytical determination of gold. A solution of gold containing 5 ppm 10 00 ml) results in interaction with a sample of aminoboran resin in continuous mode in a column At very low flow rates (0.5 ml / min). When the download is complete, the Definition; This is the gold content in the resin and it is established that the gold content in the resin can be quantified, therefore, the feasibility of using resins as an analytical method for determining the traces of gold or traces of other metals involved is established. The advantage of the proposed method is to obtain new products with improved properties, they are insoluble in water and organic solvents and are stable in a wide range of temperatures. Claims method for producing non-ionic borane resins by treating polymers with brrhydride, characterized in that, in order to obtain smolovstanoviteli, insoluble in water and organic solvents and stable at pL 1.0-8.0, as the polymer used cross-linked amine, or phosphine / containing groups of the formula -QZ (..--.: -...- 2-. J: Q-icH ,,. ,, -;.: where t, n 1, 2, 3, -.- :. o T (C, - c - NH-, - OR p,. R, R 2 is hydrogen, C.-: 0-alkyl, 2., and the treatment is carried out in a protic mineral acid, in a proton solvent, followed by poly EPA alkali metal boron hydride information sources, the received note in the examination Patent IAM l № 3609191, cl 260-583 A, published 12/07/71 (prototype)......:.