SU274356A1 - METHOD OF OBTAINING POLYACRYLONITRI.P - Google Patents

Description

A known method of producing polyacrylonitrile is by polymerizing or jurionitrile or copolymerising it with vinous monomers in a solvent medium for polymer 1 at a temperature of -80 to + 40 ° C in the presence of organic catalysts of alkali metals, such as butyl lithium, as catalysts.

However, the use of utility as a catalyst results in a low, low-yield Omolek-linear half-measure.

The proposed method is characterized in that, as a catalyst, the alkali metal alkoxides of a-hydroxyalkylamines are added or their complex compounds with alkylamides of organic k-slot. This gives the opportunity to produce high molecular weight polymers in high yield.

The catalysts can be obtained by the interaction of amides of acids (preferably L, N-substituents, for example, dimethylformamide (DMF) or d. Methyl acetamide) with metals or alkyls of metals. The first group

/-ABOUT

RC (OMe) NRs

NRs

(oily, (valeric or others) or ketones (for example, a-netopom) MeNR2 + R RCO-R RC (OMe) NR2 (R and R-al »yl, aryl or hydrogen, R - lkil or aryl. Me -metal

first group). Complex compounds of alkoxyalkyl amines are obtained by treating the latter with N, N-3aMemeHHbnni acid amides (for example, dimethylformamide or dimethyl acetal). A-oxyalkyl amines, which are not additionally treated with acid amide, when using AH as a polymerization catalyst, result in the formation of a partially insoluble in DMF polymer, and the polymerization reaction often does not reach the end. If they are kept for a long time or heated with K, -substituted acid amide and used as a homogeneous solution as catalysts, then the polymerization reaction

proceeds almost to the end. Poll-chaasi polymer, well soluble in DMF, given by the molecules of pnOGO weight.

Methods for the preparation of the catalyst. 1. From al: kilogram or aryl metals.

In a two-horn ampoule, pre-evacuated and heated to remove moisture and oxygen adsorbed on the walls, the distillate is pre-dispersed and aged over calcium hydride DMF. Then

The amount of alyl or aryl of the metal in the solvent (e.g., geus, petroleum ether, tetragdrofuran) is added neces- sarily.

Hexane, lithium ether or tetrahydrofuranium are safely fenced off, and the a-oxyalkylkylamine alcoholate, after 7-10 days, with occasional shaking, goes into DMF. AFTER DETERMINATION The total alkalinity of the catalyst is used for polymerization, considering the normal solution to be luminous. The formation of a uniform paiCTiBopa can be accelerated} Heating 1 to 1 up to 80-120 ° C for 5-30 lyn. The formation of a solid alcoholic alcohol can be avoided by adding pacTiBOip alkyl alkyl or aryl metal to hot (120 ° C) DMF. The solvent (hexane, lefthol ether, tetrahydrofuran) is immediately evaporated, and the a-avsialkylamine alcoholate goes into solution. Olerci lasts 10-15 minutes. The catalyst does not lose active 2–3 months.

2. From amides of metals.

In a two-horn ampoule prepared according to cnoicoi6y 1, the required amount of a1mide (preferably Y, N-mixed, dimethylamide nano-example) of an alkaline metal of the first ripynnbi is broken, and a solvent (“ an equimolecular amount of aldehyde (e.g., oil, valerian, etc.) is added. The reaction proceeds with a slight warming of 10 minutes. The filtered solution is poured into DMF, and then does not act as a syringe 1.

3. From the metals of the first Grull.

In a two-horn vial iodine prepared according to sioosse 1, DMF is not stirred up, and freshly cut metal is added to it when inert gas is blown. With weak reheating (40-50 ° C) and shaking, the reaction takes 20 minutes. Alcohol is formed with diamine-01xialum ilamine.

The polymerization is carried out in a solution of DMF at a temperature of from -80 to -10 ° C, preferably from -60 to -40 ° C. A solution of the catalyst in DMF or dimethylacetamide is introduced into the polymerization mixture of 0.3-3.0 gm / l of AN and DMF while blowing inert gas. The polymerization reaction takes less than 10 minutes. PacTiBQp is stabilized by adding 5-10 ml of DMF with 1-2 callae of concentrated sulfuric acid. A viscous colorless homogeneous solution of the polymer is formed which, after concentration (if necessary) of the paicTB remover to 12-18 / a-th solution and filtering, can be used to form the fibers. The distilled solvent is again used in the polymerization reaction. The molecular weight is controlled by varying the concentration (monomer, catalyst concentration and temperature. The polymer can be precipitated by pouring the reaction mass (after

breakage of the imerization process) into water. The polymer yield 95-1007, its mol. weight is from 50 to 600 thousand, it has a narrow p-weight distribution, nitrogen content is 26.6 per cent. The strength of fibers formed in an organic bath is up to 60 bits. km, lengthening 10 150/0.

Typical olyth

In a heated three-neck flask with a stirrer heated by a gas burner, DMF and AN were dried over calcium hydride. The temperature of the experiment is brought to the temperature of the experiment and by blowing an inert gas at

stirring, pour in a solution of the catalyst in DMF. After 3 min, the process is terminated by adding a solution of concentrated sulfuric acid in DMF. A viscous, colorless, homogeneous polymer solution is obtained.

Example 1. To 25 ml of DMF LRI -60 ° C, with a wall, 2 ml of a 1.8-n hexane solution of H-butnllithium were wall-coated. Temieraturu brought to komiaty and carefully drove away hexane. After 10 days, a homogeneous solution of the catalyst with an alkalinity of 0.26 N, which corresponds to 0.3 g-mol / l, was obtained by iriodical shaking. 85 ml of DMF and 6.0 ml (0.99 g-mol / l) AN were distilled into the flask. At -60 ° C, 0.66 ml (0.001 g-mol / l) of catalyst was added. After 3 minutes, 5 ml of DMF was added with 1 cup of concentrated sulfuric acid. Got a colorless homogeneous solution of lolimer. You: move 100o / o, 8.

PRI and: m e r 2. To 13 ml of DMF LRI 100 ° C LRI

A purge of argon was added gradually with 2 ml of a 1.8-1N hexane solution of H-butyl lithium. The resulting paiCTBop was kept at this temperature for 5 minutes. Its alkalinity was 0.34H, which corresponds to 0.17 mol / l catalyst a.

In a flask with a stirrer, distilled 85 ml of DMF and 6.0 ml (0.99 g-mol / l) of AN. The temperature was brought to -60 ° C and Lrilili 0.6 ml (0.0012 g-lul / l) of catalyst. Temleraturu

and weak stirring was maintained for 3 minutes, then 5 L 1. l DMF was added with 1 callae of concentrated sulfuric acid and mixed well. 55 ml of DMF were distilled off under vacuum to warm up to 60 ° С, and the hot solution

filtered through a No. 2 glass filter and formed into fibers in a glycerin and DMF bath (1: 1) at room temperature. This was followed by stretching in glycerin at 140 ° C. At a 20-fold stretch, we obtained fiber with No. 1220, strength 65 bits. km and an elongation of 13%. The polymer had i) 2.5. The yield of the polymer was SO2 / Example 3. Nz 55 ml of distilled off from the previous experiment, aged for 2 days over calcium hydride, were for the first time 5 ml removed and discarded, and the next 50 ml were dropped into a lolimerization flask. 4.0 L1l (1.1 g-lul / l} AH was distilled there, the temperature was brought to -60 ° C and poured with 0.35 ml (0.0012 g-mol / l)

The temperature and weak stirring were maintained for 3 minutes, then 3 ml of DMF was added with 1 drop of Rroro bath, sulfuric acid bath and stirred well. 30 ml of the solvent were distilled under vacuum while heating to 60 ° C. Then we did the same as in example 2. We received a wave of-oh-the-young with a strength of 60 bits. "M, elongation 12o / o. Polymer 100Vo output, t1 2.58.

Example 4. In a polymerization flask were poured through a glass 1N filter N ° 3 with 50 ml of DMF aged over calcium hydride. A vacuum was created in the flask and the reaction was continued for 5 minutes. Then 5.5 L1L (1.46 g-mol / l) AN were distilled. The temperature was brought to -60 ° C and 0.7 ml (0.0024 g-mol / l) of catalyst (| see example 2) was added while mixing by stirring. After 5 minutes, 50 ml of DMF with 2 drops of concentrated sulfuric acid were added, stirred until a homogeneous solution, and poured into water with stirring. The half-chamber was filtered, washed with water and dried to constant weight at 60 ° C. The polymer yield 100%, t1 2,73. A fiber was formed from a 140 / st polymer solution in DMF as in Example 2. The fiber strength was 50 dis. ky, elongation 15 / o Example 5. 85 ml of DMF-6.07 IL (0.99 g-mol / l) AN were distilled into the polymerization flask. The omesis temperature reached -60 ° C and without additional external cooling 0.5 ml (0.001 g-mol / l) of catalyst was added (see example 2). After 3 min, temperature B in the flask rose to -16 ° C (a drop of 44 °). By adding 5 ml of DMF with 1 drop of concentrated sulfuric acid polymerizate into water. The polymer was filtered, washed (WATER and dried to noiCTOHHiHoro weight at 60 ° C. The output of the polymer was YOa / o, T1 2.8.

Example 6. 60 ml of DMF was distilled into the ampoule and at 120 ° C, 8 ml of a 1.8-n hexane solution of H-butyllIITI were added. After 10 min, the solution was cooled with running water. A 0.38-n catalyst solution was obtained, which corresponds to a co-concentration of 0.19 g-mol l.

In a three-neck flask with a capacity of 1 l were distilled. On a laboratory column under vacuum, 800 ml DMF and 55 ml AH, aged 3 days over calcium hydride. The temperature of the mixture was brought to -70 ° С, external cooling was stopped, and the flask was wrapped in a wool case. 8.4 ml (0.002 g-mol l) of catalyst was added. After 3 minutes, the temperature in the flask rose to -23 ° C (a drop of 47 °). By adding 20 drops of concentrated sulfuric acid in 10 ml of DMF, a colorless homogeneous polymer solution was obtained. Yield 100%, g) 2.6.

Example 7. 0.64 g (0.0125 mol) of lithium dimethylamide was placed in a double-horn ampoule blown with argon gas heated with a flame of a gas burner, 20 ml of hexane and 0.9 g (1.1 ml of 0.0125 mol) and oil were added aldehyde. At the end of the reaction, as seen by the disappearance of the lithium dimethylamide precipitate, the solution

filtered through a No. 4 glass filter. i ml of the filtered solution was added to 16 ml of DMF at 80 ° C, while blowing argon and heated for 30 minutes. A 0.12-n (0.06 mol / L) catalyst solution was obtained. 50 ml of DMF and 3.6 ml (1 g-mol / l) of AN were distilled into the polymerization flask. The temperature was brought to -60 ° C and poured 0.8. Ifl (0.001 g, 1 July / L) of the catalyst solution. Temperature and weak

stirring was maintained for 3 minutes, then the reaction was stopped by the addition of 5 ml of DMF with 1 drop of concentrated sulfuric acid. The polymer was dropped into the water. The output of the polymer SHO / o, t | 2.8. From the 14E / O-HOW polymer solution in .CMFA, the fiber was molded as in Example 2. The strength of the fiber is 55 bits. km, elongation 12 ° / o.

Example 8. A vacuum ampoule heated with a gas burner flame was distilled into 18 ml of DMF, 0.067 g of lithium was introduced in an argon blow and shaken easily. Keeping the mixture for 20 minutes at 40 ° C, 0.95-n (0.475 mol / l catalyst solution was obtained.

50 ml of DMF and 3.6 ml (I g-mol / l) of AN were distilled into the flask. The temperature was brought to 0 ° C and 0.53 ml (0.005 gm / l) of catalyst was added. After 3 min, the reaction was stopped with 5 ml of DMF

with 3 drops of concentrated sulfuric acid. Polymer yield 100%, 1 2.8.

Example 9. 10 ml of DMF was distilled into a two-horn ampoule and 4 ml of a 0.86-n solution of naphthalene sodium in tetrahydrofuran were gradually added. The tetrahydrofuran was carefully removed, and the contents of the ampoule were kept for 9 hours at 80 ° C. A 0.5-n solution was obtained, which corresponds to a catalyst concentration of 0.25 g-lulb / l. The flask was distilled 50, DMF silt

and 3.6 ml (1.0 g-mol / l) of AN. At -60 ° C, 0.2 ml (0.001 g-mol / l) of the catalyst solution was added. After 3 hours, 5 ml of DMF was added with 1 drop of concentrated sulfuric acid. The polymer was planted in water, washed with water,

alcohol, ether (from naphthalene). Vyhod was 96Vo, ill 2.62.

Example 10. In a two-horn vial was placed 0.39 g (0.0076 luli) of lithium dimethylamide and

10 ml of hexane was distilled on it. 0.45 ml (0.0062 mol) of acetone was added to the suspension. After 20 min, the solution was filtered through a No. 4 glass filter and gradually, with argon blown, it was added to 23 ml.

DMF heated to 90 ° C. Off this temperature for 20 minutes, a 0.24-n catalyst solution was obtained. 50 l / l of DMF and 3.6 ml (1.0 g-lul / l) of AN were distilled into the polymerization flask. The temperature was brought to -60 ° C and poured

0.5 ml (0.0012 g-mol / l) of the catalyst solution. After 3 min, the reaction was broken with 5 l of DMF with one drop of concentrated G. sulfuric acid. A clear, colorless, homogeneous solution of polymer was obtained. The subject of the invention is a method of producing liaacrylonitrile by polymerizing acrylic nitrile or co; polymerizing it with vinyl monomers in a solvent medium 5 for a polymer at a temperature of from -80 to -40 ° C in the presence of catalysts, characterized in that the target is pol. high molecular weight polymers with you, with their output, are used as alkaline metal alkali metal a-hydroxyalkyl. polymers or their 1M | Plexic compounds with alkylamides of organic acids.