RU2206571C1 - Method for preparing organometallohydroxy- stannates - Google Patents

Abstract

FIELD: organometallic compounds, chemical technology. SUBSTANCE: invention relates to the improved method for preparing organometallohydroxystannates of the general formula: Yalk₂SnOMⁿR_mY_n-m-1 [where M is metal taken above group Ca, Zn, Cu, Al, Si, Ge, Sn, Ti, Fe, Mn, Co, Cr; Y is OR' (R' is alkyl with 1-4 carbon atoms) or O₂CR″ (R'' is alkyl, cycloalkyl with 6-11 carbon atoms); R is alkyl with 1-4 carbon atoms, vinyl, phenyl; n means valence of metal M; m = 0-2, m n ≥ 1] by interaction of dialkyltin oxides with alkoxydes or acylates of above indicated metals M. Reaction is carried out in atmosphere of dry purified nitrogen at heating of reaction mixture at temperature 80-100 C in the presence of aliphatic or cycloaliphatic carboxylic acid as a catalyst taken in the amount 2-5% of mass of dialkyltin oxide. Method ensures to obtain reactive, thermically and hydrolytically low-stable organometallohydroxystannates with high yield and sufficiently high quality. Effectiveness of method is confirmed by its successful testing in experimental conditions. EFFECT: improved preparing method. 2 cl

Description

 The invention relates to methods for producing organometallic compounds containing Sn-O-M bond, where M is a metal selected from different groups of the Periodic system of elements, namely organometalloxystannanes.

 Compounds of this type are recommended for use as starting monomers for producing polymers, as thermal and light stabilizers for polyolefins, for imparting water-repellent properties to cement, metals, wood, fabrics, paper; as fungicides, insecticides and antibacterial agents, as catalysts or components of catalytic systems and initiators of the reactions of homo- and copolymerization of monomers of various chemical nature and to obtain composite compositions (US Pat. US 3307973, 1967, NKI 428-573; 5461139, 1995 ., MKI C 08 G 063/08; 5003015, 1991, MKI C 08 F 004/72; 5128295, 1992, MKI C 08 F 004/64; 5430125, 1995, NCI 528/354; 5034455 , 1991, MKI S 08 K 003/26).

There are very few works describing methods for the preparation of organometalloxystannanes, most of which were developed more than three decades ago [M. Dub (bd.) "Organometallic Compounds", vol. II. 1967; vol. II 1-st Suppl., 1973. Springer Verlag, Berlin-NYj. High reactivity, as well as hydrolytic and thermal instability of such compounds are a serious obstacle to their preparative synthesis. In one of the works (Beckmann J., ao - Organometallics. 1998, v.17, 26, p. 5697-5712), practically significant results were obtained by the reaction of dialkyltin oxides with organohalogenosilanes only in the case of using starting reagents with bulky tert-butyl groups and when conducting synthesis for several days at a temperature of ~ 60 ^o C.

 The methods known to us have limited and mainly theoretical significance: as a rule, their descriptions do not contain the conditions for reactions, there is no information about technological methods and quantitative results of their implementation.

An exception is the method for producing organometalloxystannans, protected by US patent 3307973 (see above), which we have chosen for the prototype. According to the invention, the above compounds expressed by the general formula
[R ₂ SnO-] _n E
(where E = MX _vn and M (R ' _m ) X _vnm , M is a metal selected from the group B, Al, Si, Ti, Zr, V, or ≡VO; X is halogen or OR ^о , R ^о is hydrocarbon or a fluorocarbon radical with 1-18C; R '- alkyl with 1-12C: v - valency M (3 or 4); m - in the range from 1 to v-1; n - from 1 to v; the sum of m + n≤ v], obtained by reacting a dialkyltin oxide with a metal halide, alkoxide, alkyl halide or metal alkyl alkoxide by heating a mixture of reaction components in an atmosphere of dry inert gas or in an inert organic solvent. The heating range of the reaction mixture is from 125 to 185 ^o C. When using A solvent was used with a boiling point <110 ^{° C. An} autoclave was used. The yield of the target product in the examples was not usually indicated, except for one, where it was 92.5%; in another example, the product yield was given in grams, which allowed us to calculate its percentage (57%).

The disadvantages of the method proposed by the author to obtain compounds protected by US patent 3307973 include the need:
1) use organic solvents with thorough thorough drying before synthesis, followed by separation of the solvents (filtration, evaporation) from the reaction products after completion of the synthesis;
2) apply the autoclave when using solvents with t. Bales. <110 ^o C, since in this case the process proceeds at elevated pressure;
3) to carry out the reaction at a temperature of 140-185 ^o C, if the solvent is not used in the process, which affects the quality of the products (tarring, the appearance of color, etc.).

We faced the task of eliminating the above technological difficulties and developing an effective way to obtain organometalloxystannans corresponding to the general formula
YAlk ₂ SnOM ⁿ R _m Y _nm-1 ,
where M is a metal selected from the group of Ca, Zn, Cu, Al, Si, Ge, Sn, Ti, Fe, Mn, Co, Cr; R is alkyl with 1-4 C, vinyl, phenyl; Y = OR '(R' is alkyl with 1-4C) or O ₂ CR "(R" is alkyl, cycloalkyl from 6-11 C); Alk is alkyl with 1-8C; n is the valence of the metal M, m = 0-2, nm≥1.

The problem is solved in that we have proposed a method for producing the above compounds by the interaction of dialkyltin oxides (Alk ₂ SnO) _x with alkoxides or acyloxy derivatives of metals M ⁿ R _m Y _nm taken in equimolar ratio; the process is carried out by heating the reaction mixture to a temperature of 80-100 ^o C in the presence of a catalyst - a carboxylic acid of the general formula ZCO ₂ H, where Z is alkyl or cycloalkyl with 3-11 C, in an atmosphere of dry purified nitrogen. The amount of catalyst is 2-5 wt.% Of the amount taken in the reaction of dialkyltin oxide.

 Details of the practical implementation of the method can be illustrated by the following examples. All reactions were carried out in an atmosphere of dry purified nitrogen.

 Example 1. Obtaining tetrabutyl dicaprylate distannoxane.

Into a three-necked flask equipped with a thermometer, stirrer and reflux condenser, 26.4 g (0.106 mol) of dibutyltin oxide, 55 g (0.106 mol) of dibutyltin dicaprylate and 0.53 g of caprylic acid are charged. The reaction mixture is stirred at a temperature of 80-90 ^o C until complete dissolution of dibutyltin oxide (about 55 minutes). The result is 81 g (99.5%) of tetrabutyl dicapryloxydistannoxane n _D ²⁶ 1.4872-1.4875, the tin content of 30.7-30.9%.

 Example 2. Obtaining dibutylbutoxy (tributoxytitanoxy) stannane.

Under conditions similar to those described in example 1, from 13.6 g (0.04 mol) of tetrabutoxy titanium and 9.95 g (0.04 mol) of dibutyltin oxide in the presence of 0.41 g of caprylic acid (reaction temperature 90 ^° C, time 35 min), 23 g (97.7%) of dibutylbutoxy (tributoxytitanoxy) stannane are obtained. n _D ²⁶ 1.4959-1.4974, tin content 20.0-20.2%.

 Example 3. Obtaining dibutylethoxy (triethoxysiloxy) stannane.

Under conditions similar to those described in example 1, from 35.8 g (0.144 mol) of dibutyltin oxide and 30 g (0.144 mol) of tetraethoxysilane in the presence of 1.79 g of caprylic acid (reaction temperature 100 ^{° C.} , time — 50 minutes), 64 are obtained. 9 g (98.6%) of dibutylethoxy (triethoxysiloxy) stannane. The tin content is 25.8-26.1%.

Example 4. Obtaining dibutylmethoxy (methylvinylmethoxysiloxy) stannane
Under conditions similar to those described in example 1, from 94 g (0.378 mol) of dibutyltin oxide and 50 g (0.378 mol) of methyl vinyl dimethoxysilane in the presence of 4.7 g of caprylic acid (reaction temperature 100 ^{° C.} , 4 hours), 143 g (99 , 3%) dibutylmethoxy (methylvinylmethoxysiloxy) stannane, tin content 30.9-31.2%.

Example 5. Obtaining dibutylethoxy (methylphenylethoxysiloxy) stannane
Under conditions similar to those described in example 1, from 94 g (0.378 mol) of dibutyltin oxide and 77.6 g (0.378 mol) of methylphenyl diethoxysilane in the presence of 4.7 g of lauric acid (reaction temperature 85-90 ^o C, time - 4 hours) receive 171 g (97%) of dibutylethoxy (methylphenylethoxysiloxy) stannane, tin content 25.9-26.2%.

Example 6. Obtaining dibutylcaprylate (dicaprylateferrooxy) stannane
Under conditions similar to those described in example 2, from 2.38 g (0.01 mol) of dibutyltin oxide and 4.65 g (0.01 mol) of iron tricaprylate in the presence of 0.1 g of caprylic acid (reaction temperature 95-100 ^o C , time - 50 min) 6.58 g (93.6%) of dibutylcaprylate (dicaprylateferrooxy) stannane are obtained. The tin content is 15.9-16.3%.

Example 7. Obtaining dimethyl (2-ethylhexanate) (2-ethylhexanatecalciumoxy) stannane
Under conditions similar to those described in example 2, from 3.29 g (0.02 mol) of dimethyltin oxide and 6.53 g (0.02 mol) of calcium octoate in the presence of 0.07 g of 2-ethylhexanoic acid (reaction temperature 85-95 ^o C, time — 40 min) 9.43 g (96%) of dimethyl (2-ethylhexanate) (2-ethylhexanate-calcium-oxy) stannane are obtained. The tin content is 24.1-24.3%.

Example 8. Obtaining dimethyl (2-ethylhexanate) (2-ethylhexanate zincoxy) stannane
Under conditions similar to those described in example 2, from 3.29 g (0.02 mol) of dimethyltin oxide and 7.04 g (0.02 mol) of zinc octoate in the presence of 0.07 g of 2-ethylhexanoic acid (reaction temperature 95-100 ^o C, time - 50 min) 9.81 g (95%) of dimethyl (2-ethylhexanate) (2-ethylhexanate zincoxy) stannane are obtained. The tin content is 22.7-23.1%.

Example 9. Obtaining dimethylisobutoxy (diisobutoxyaluminoxy) stannane
Under conditions similar to those described in example 3, from 3.29 g (0.02 mol) of dimethyltin oxide and 4.93 g (0.02 mol) of triisobutoxyaluminium in the presence of 0.07 g of butyric acid (reaction temperature 94-98 ^o C, time - 60 min), 7.64 g (93%) of dimethylisobutoxy (diisobutoxyaluminoxy) stannane are obtained. The tin content is 28.7-29.1%.

Example 10. Obtaining dibutylisobutoxy (diisobutoxychromoxy) stannane
Under conditions similar to those described in example 2, from 2.38 g (0.01 mol) of dibutyltin oxide and 2.71 g (0.01 mol) of triisobutoxyaluminium in the presence of 0.07 g of butyric acid (reaction temperature 80-90 ^o C, time - 50 min), 4.64 g (91.2%) of dibutylisobutoxy (diisobutoxychromoxy) stannane are obtained. The tin content of 23.1-23.5%.

Example 11. Obtaining dimethylcyclopentyl acetate (cyclopentyl acetate-manganese) stannane
Under conditions similar to those described in example 2, from 3.29 g (0.02 mol) of dimethyltin oxide and 6.19 g (0.02 mol) of manganese cyclopentyl acetate in the presence of 0.07 g of cyclopentylacetic acid (reaction temperature 85-95 ^o C , time - 55 min), 9.0 g (95%) of dimethylcyclopentyl acetate (cyclopentyl acetate manganese) stannane are obtained. The tin content is 24.9-25.2%.

Example 12. Obtaining dibutylcyclopentyl acetate (cyclopentyl acetate-cobaltoxy) stannane
Under conditions similar to those described in example 1, from 2.38 g (0.01 mol) of dibutyltin oxide and 3.13 g (0.01 mol) of cobalt cyclopentyl acetate in the presence of 0.07 g of cyclopentylacetic acid (reaction temperature 95-100 ^o C , time - 40 min), 5.26 g (95.5%) of dibutylcyclopentyl acetate (cyclopentyl acetate cobaltoxy) stannane are obtained. The tin content is 21.3-21.6%.

Example 13. Obtaining dioctylcyclopentyl acetate (cyclopentyl-acetate-copper) stannane
Under conditions similar to those described in example 1, of 3.61 g (0.01 mol) of dioctyltin oxide and 3.18 g (0.01 mol) of copper cyclopentyl acetate in the presence of 0.07 g of cyclopentylacetic acid (reaction temperature 94-100 ^o C , time - 40 min), 6.52 g (96%) of dioctylcyclopentyl acetate (cyclopentyl acetate medoxy) stannane are obtained. The tin content of 17.3-17.6%.

Example 14. Obtaining tetrabutyl dicaprylate distannoxane
A jacketed 400-liter reactor equipped with a thermometer, stirrer and reflux condenser was charged with 77.26 kg of dibutyltin oxide, 160.98 kg of dibutylstannandicaprilate and 1.76 kg of caprylic acid. The reaction mixture is stirred at a temperature of 90 ± 10 ^o With until complete dissolution of dibutyltin oxide (about 2 hours). The result is 228.47 kg (95.9%) of tetrabutyl dicaprylate distannoxane. n _D ²⁶ 1.4874, tin content of 30.8%.

 Example 15. Obtaining dibutylethoxy (triethoxy germanyoxy) stannane.

Under conditions similar to those described in example 1, from 23.8 g (0.1 mol) of dibutyltin oxide and 23.7 g (0.1 mol) of tetraethoxy german in the presence of 0.95 g of caprylic acid (reaction temperature 85-95 ^o C, time - 50 minutes) receive 46.3 g (97.5%) of dibutylethoxy (triethoxy germanyoxy) stannane, the tin content of 24.8-25.1%.

 As a result of the study of patent documentation and scientific and technical literature, we did not find materials that would discredit the novelty of the proposed method. The latter has several advantages compared with the prototype, represents a step forward compared to the known method and corresponds to the inventive step. The method has been successfully implemented in pilot production.

 Thus, the proposed technical solution meets the criteria of patentability.

Claims (2)

1. The method of obtaining organometalloxystannanes of the General formula
YAlk ₂ SnOM ⁿ R _m Y _nm-1 ,
where M is a metal selected from the group Ca, Zn, Cu, Al, Si, Ge, Sn, Ti, Fe, Mn, Co, Cr;
Y is OR '(R' is alkyl with 1-4C) or O ₂ CR "(R" is alkyl, cycloalkyl with 6-11C);
Alk is alkyl with 1-8C;
R is alkyl with 1-4C, vinyl, phenyl;
n is the valency of the metal M;
m is 0-2;
nm≥1,
characterized in that the dialkyltin oxide is reacted with organometallic compounds of the formula
M ⁿ R _m Y _nm ,
where M, R, Y, m, n have the above meanings,
at a temperature of 80-100 ^o With in the presence of a catalyst - a carboxylic acid of the General formula
ZCO ₂ H, where Z is alkyl or cycloalkyl with 3-11C,
in an atmosphere of dry purified nitrogen.  2. The method according to claim 1, characterized in that the catalyst is added to the reaction mixture in an amount of from 2 to 5% by weight of dialkyltin oxide.