RU1358350C - Method of synthesis of organometallic compounds - Google Patents

Abstract

FIELD: polymeric organometallic compounds. SUBSTANCE: modified polynaphthylenemethylene containing hydroxyl and acetoxyl groups at concentrations 1-4 and 1-9 wt.-%, respectively, is used as polymer. Before interaction with alkaline metal polymer can be treated with organometallic compound selected from the group: polynaphthylenemethylene potassium, butyllithium, triisobutylaluminium or diisobutylaluminium hydride at concentration 0.01-0.20 mole/mole polynaphthylenemethylene. EFFECT: increased yield and stability of polymeric organometallic compound. 2 cl

Description

 The invention relates to a method for producing polymeric organometallic compounds (MOS) used as initiators of anionic polymerization of diene and vinyl aromatic monomers.

 The purpose of the invention is to increase the yield and stability of polymer MOS.

Взаимодействие модифицированногоо ПНМ с щелочным металлом протекает в нескольких направлениях:
1. Образование полимерного МОС анионрадикальной структуры

M⁺ , где М - атом щелочного металла.The essence of the invention lies in the fact that the polymer used is modified polynaphthylenemethylene (PNM) containing functional hydroxyl and acetoxy groups in an amount of 1-4 and 1.9 wt.%, Respectively

The interaction of the modified PNM with an alkali metal proceeds in several directions:
1. The formation of polymer MOS anionradical structure

M ⁺ , where M is an alkali metal atom.

3. Восстановление ацетоксигруппы МОС с последующим образованием металлнафтилоксида

Превращение обеих функциональных групп в алкоксипроизводные металлов может быть также проведено предварительной обработкой полинафтиленметилена заранее приготовленным калийполинафтиленметиленом или другим МОС, например бутиллитием, триизобутилалюминием или диизобутилалюминийгидридом, в количестве 0,01-0,2 моль на 1 моль модифицированногоо полинафтиленметилена.2. Substitution of hydroxyl hydrogen with an alkali metal atom under the action of a metal or formed MOS

3. Recovery of the acetoxy group of the MOC with the subsequent formation of metal naphthoxide

The conversion of both functional groups to alkoxy derivatives of metals can also be carried out by pretreating polynaphthylenemethylene with pre-prepared potassium polynaphthylenemethylene or other MOC, for example, butyl lithium, triisobutylaluminum or diisobutylaluminum hydride, in an amount of 0.01-0.2 mol per 1 mol of modified methylenemethylene.

Example 1. In a three-necked flask in an atmosphere of dry nitrogen, 45 g of modified polynaphthylenemethylene (mol. 450) containing 1 wt.% Hydroxyl and 1 wt.% Acetoxyl groups, 300 ml of tetrahydrofuran and 23 g of sodium in the form of a wire with a diameter of 1.5 mm. The reaction is conducted at ²⁰ ° C for 6 hours. The resulting solution was transferred into a Schlenk vessel.

Analysis of a solution of organometallic compounds:
The content of total sodium, g-eq / l 0.606
Content "asset-
nogo "sodium, g-eq / l
(i.e. sodium bound
go in the form of a cation
with anion radical
naphthalene link) 0.520 Yield,% 60
After storing the solution for one month at ²⁰ ° C the content of "active" sodium-eV 0.50 g / l.

 Example 2. Under the conditions of Example 1, a polynaphthylenemethylene resin containing 4 wt.% Hydroxyl and 1 wt.% Acetoxy groups was treated with sodium.

Analysis of a solution of organometallic compounds:
The content of total sodium, g-eq / l 0.89
The content of "active" sodium, g-equiv / l 0.68 Yield,% 78
After storing the solution for 1 month GNSO 20 ^C content of the "active" sodium 0.67 g-eq / l.

 Example 3. Under the conditions of Example 1, a polynaphthylenemethylene resin containing 1 wt.% Hydroxyl and 9 wt.% Acetoxy groups was treated with sodium.

Analysis of the resulting solution of organometallic compounds:
The content of total sodium, g-eq / l 1,073
The content of "active" sodium, g-equiv / l 0.635 Yield,% 73
After storage for 1 month at 20 ^about With the content of "active" sodium of 0.62 g-equiv / L.

 PRI me R 4. Analogously to example 1, carry out the reaction of interaction of polynaphthylenemethylene containing 4 wt. % hydroxyl and 9 wt.% acetoxy groups, with metallic sodium.

Analysis of the resulting solution of organometallic compounds:
The content of total sodium, g-eq / l 1.26
The content of "active" sodium, g-equiv / l 0.696 Yield,% 80
After storage for 1 month at 20 ^about With the content of "active" sodium of 0.68 g-equiv / L.

Example 5. In a three-necked flask in an argon atmosphere, 45 g of polynaphthylenemethylene (mol% 500) containing 4 wt.% Hydroxyl and 9 wt. % acetoxy groups, 300 ml of tetrahydrofuran and 16 g of lithium in the form of a wire with a diameter of 1.5 mm After 6 hours (20 ° ^C) solution prepared organolithium compound.

Analysis of a solution of organometallic compounds:
The content of total lithium, g-equiv / l 1.30
The content of "active" lithium, g-eq / l 0.730 Yield,% 80
After storage for 1 month, the concentration of "active" lithium is 0.51 g-eq / L.

 PRI me R 6. Analogously to example 5, using 4,4-dimethyl-1,3-dioxane as a solvent, a solution of lithium polynaphthylenemethylene is obtained.

Analysis of a solution of organometallic compounds:
The content of total lithium, g-eq / l 1.21
The content of "active" lithium, g-eq / l 0.64 Yield,% 70
After storage for 1 month, the content of "active" lithium is 0.51 g-eq / L.

 PRI me R 7. Analogously to example 5, using as a solvent a mixture of 210 ml of tetrahydrofuran and 90 ml of toluene, get a solution of lithium polynaphthylenemethylene.

Analysis of a solution of organometallic compounds:
The content of total lithium, g-eq / l 1,218
The content of "active" lithium, g-eq / l 0.648 Yield,% 71
After storage for 1 month, the content of "active" lithium is 0.59 g-eq / L.

 Example 8. In a three-necked flask, a solution of 45 g of polynaphthylenemethylene (mol. 450) containing 1 wt.% Hydroxyl and 9 wt.% Acetoxyl groups, 300 ml of tetrahydrofuran was charged, purged with argon, 10 g of potassium were added, after 6 hours, the resulting solution was analyzed.

Analysis of a solution of organometallic compounds:
The content of total potassium, g-equiv / l 1.27
The content of "active" potassium, g-equiv / l 0.701 Yield,% 80
After storage for 1 month, the content of "active" potassium is 0.689 g-eq / L.

 PRI me R 9. In a three-necked flask in an argon atmosphere, 45 g of polynaphthylenemethylene containing 4 wt.% Hydroxyl and 9 wt.% Acetoxyl groups, 300 ml of THF are charged. A solution of potassium polynaphthylenemethylene (0.12 mol) obtained according to Example 8 is added portionwise to the resulting mixture until a blue color disappears, then 20 g of sodium are charged in the form of a wire, after 4 hours the solution is separated and analyzed.

Analysis of a solution of organometallic compounds:
The content of total potassium and sodium, g-equiv / l 0.699
The content of "active" sodium, g-equiv / l 0.390 Yield,% 80
After storage for 1 month at ²⁰ ° C the content of "active" sodium 0.37 g-eq / l.

Example 10. In a three-necked flask in an inert gas atmosphere, 45 g of polynaphthylenemethylene containing 4 wt.% Hydroxyl and 9 wt.% Acetoxy groups are dissolved in 300 ml of tetrahydrofuran. Was added portionwise 130 ml with a concentration of 1.5 mol / L solution of n-butyllithium in toluene was added after 1 h 20 g of sodium in the form of wire, the mixture was incubated 4 hours at ²⁵ ° C, the resultant solution was analyzed.

Analysis of a solution of organometallic compounds:
General content
lithium and sodium, g-equiv / l 0,905
The content of "active" sodium, g-eq / l 0.505 Yield,% 80
The solution is stable during storage for 2 months.

 Example 11. To the solution of polynaphthylenemethylene obtained in Example 10, 0.2 mol (40 g) of triisobutylaluminium was added portionwise with cooling, 20 g of sodium wire was charged, it was incubated for 4 hours, and the sodium compound solution was separated.

Analysis of a solution of organometallic compounds:
The content of "active" sodium, g-equiv / l 0.58 Yield,% 78
After storage for 1 month, the content of "active" sodium is 0.55 g-eq / L.

 PRI me R 12. In the conditions of example 11, using 0.01 mol of triisobutylaluminum, get a solution of the sodium compound with a total sodium content of 1.19 g-equiv / l and an active sodium of 0.675 g-equiv / l. Yield 79%.

 The solution is stable for 1 month.

 Example 13. Under the conditions of Example 4, using a mixture of 90 ml of tetrahydrofuran and 210 ml of toluene as a solvent, an organic sodium compound was obtained.

Analysis of a solution of organometallic compounds:
The content of total sodium, g-eq / l 1,051
The content of "active" sodium, g-eq / l 0.487 Yield,% 56
After storage for 2 months, the content of "active" sodium is 0.44 g-equiv / L.

 PRI me R 14. In the conditions of example 11, using 0.2 mol of diisobutylaluminium hydride, get a solution of the sodium compound with the content of "active" sodium 0.60 g-equiv / l, yield 80%.

 The solution does not change activity for 2 months.

 Obtained by the proposed method, MOS are soluble in polar solvents and their mixtures with aromatic hydrocarbons. Their solutions are intensely colored and give an EPR signal with the q-factor of the free electron. They are the initiators of the polymerization of dienes and styrene, as illustrated by the following data.

The polymerization of butadiene is carried out in cyclohexane solution at a monomer concentration of 1.35 mol / l, litiypolinaftilenmetilena 1,7˙10 ^-3 mol / l and a temperature of 50 ^C. The yield of polybutadiene, for 3 hours 100%, molecular weight: 384000.

In toluene, at an initial concentration of 3.15 mol / L monomer and sodium naphthylenemethylene (see Example 1), 1.33 x 10 ^-4 mol / L are obtained in 100% polymer with a mol.m yield. 10700 instead of the calculated 1280000 due to chain transfer to toluene.

In a stirred reactor charged with 2175 g of toluene and 65 ml of a solution natriypolinaftilenmetilena obtained in Example 13. In a machine working mixer for 2 hours at 60 ° ^C is fed a mixture of 1987 g of butadiene and 662 g of styrene, 1740 g of toluene. Monomer conversion 100%, intrinsic viscosity of the copolymer [η] = 0.1 dl / g; the microstructure of the butadiene part of the polymer: the content of 1,4 units of 51%, 1,2 units of 49%.

Claims (2)

 1. METHOD FOR PRODUCING METAL-ORGANIC COMPOUNDS by reacting alkali metals with polymers containing aromatic structures in an environment of polar solvents or a mixture of polar solvents with hydrocarbon solvents, characterized in that, in order to increase the yield and storage stability of organometallic compounds, a modified polynaphthylenemethylene is used as a polymer containing 1-4 wt.% hydroxyl groups and 1-9 wt.% acetoxyl groups.  2. The method according to p. 1, characterized in that before contact with the alkali metal, the modified polynaphthylenemethylene is treated with an organometallic compound selected from the group consisting of potassium polynaphthylenemethylene, lithium butyl, triisobutylaluminum, diisobutylaluminum hydride, in an amount of 0.01-0.020 mol of polymethylenemethylene .