Method of preparing catalytic component, catalytic component, method of preparing catalytic complex, catalytic complex, method of production of butadiene (co)

FIELD: polymer production and polymer production catalysts.

SUBSTANCE: invention relates to synthesis of catalysts for production of cis-polybutadiene and butadiene/isoprene cis-copolymer, which can be employed in synthetic rubber industry. Task of invention resides in providing a novel method for synthesis of high-activity catalytic component, in particular neodymium neodecanoate, by reaction of neodymium oxide with neodecanoic acid in presence of metal chloride catalysts characterized by low acidity enabling conduction of process in stainless steal apparatuses and so making it possible to exactly controlling molar ratio of neodymium neodecanoate to free neodecanoic acid and water. Catalytic complex is formed by mixing neodymium neodecanoate-based catalytic component with butadiene, triisobutylaluninum, and diisobutylaluninum hydride in hydrocarbon solvent. Polymerization of butadiene or copolymerization of butadiene with isoprene is carried out in presence of thus formed catalytic complex in hydrocarbon solvent.

EFFECT: increased percentage of cis-1,4 units in polybutadiene or butadiene/isoprene copolymer and narrowed polymer or copolymer molecular weight distribution.

11 cl, 1 tbl, 45 ex

 

The invention relates to a process for the synthesis of catalysts for production of 1,4-CIS-polybutadiene, 1,4-CIS-copolymers of butadiene with isoprene and can be used in the synthetic rubber industry, and the resulting polymers - in tire and rubber industry.

In recent years, energy-saving technologies and environmental protection are becoming increasingly important. On the market there is an increasing demand for vehicles with lower fuel consumption and technical design using materials having high wear resistance and strength. Increased requirements from the side of the tire industry. Low rolling resistance and high wear resistance - the two main directions in the production of tires. Polybutadiene with a high content of CIS-links found its wide application in the tire industry, responding to the above stated requirements. Molecular weight of the polybutadiene, the polydispersity, the content of CIS-links are key indicators from the point of view of operational properties of these polymers. Current research is directed mainly to the development of new catalytic systems and obtaining polymers with high stereospecificity. Polybutadiene with a high content of CIS-get links using stereospecific catalysts C is glare-Natta-based ORGANOMETALLIC complexes of transition and rare earth metals. The polymers obtained with the use of catalytic systems based on rare-earth metals, have better machinability, wear resistance, tear resistance and other indicators do not contain oligomers and therefore non-toxic.

U.S. patent 5220045 describes how to obtain polymers with the use of catalytic complexes on the basis of metal carboxylates, synthesized by the reaction of aqueous solutions of nitrates of the metals with carboxylic acid dissolved in the hydrocarbons under the action of ammonia or amines. This method allows you to get the neodymium carboxylates with high yield, high purity and catalytic activity. This multi-stage process (receipt of oxide of neodymium nitrate, neodymium, receipt of nitrate of neodymium neodymium carboxylate, rinsing solution of neodymium carboxylate with water, drying the resulting solution) and it can be done only in expensive enameled equipment due to the high acidity of solutions of neodymium nitrate (pH 0-0,6). Furthermore, this process is characterized by a large number of waste products, due to the method of obtaining (3 mol of nitrate and 1.5-2 mol of amine to 1 mol of neodymium carboxylate is to neutralize the environment take the excess amine). These factors significantly increase the cost of the process received the I of the neodymium carboxylate, and trace amounts of extraneous metals (due to the destruction of the walls of the apparatus and pipelines at the intersection of the solutions of nitrates or nitric acid with a metal surface) reduce the quality of the target product.

Closest to the technical nature of U.S. patent 6482906, which describes how to obtain 1,4-CIS-polybutadiene using a catalytic system based on neodecanoate neodymium synthesized by direct contact oxide neodymium neodecanoate acid in hydrocarbon environments in the presence of a small amount of water and hydrochloric acid. This method allows to obtain neodecanoate neodymium in the apparatus of stainless steel at low reagent consumption and minimal waste production. Obtained in this way neodecanoate neodymium has a sufficiently high catalytic activity. However, this product does not exceed 75-91% neodymium and 67-82% neodecanoic acid. In the synthesis process, it is difficult to achieve a consistent composition of the target product (stable ratio neodecanoate neodymium: free acid: water)as recovered in the synthesis of hydrochloric acid displaces the weaker neodecanoate acid salt and its content in the catalyst is difficult to regulate. In addition, in the above method of obtaining neodecanoate neodymium not decree what about how to handle waste, contain neproreagirovavshimi the neodymium oxide, hydrochloric acid, insoluble resinous substance and water. The interaction of the oxide with neodymium neodecanoate acid occurs in the presence of hydrochloric acid, diluted to low concentrations (catalytic amounts). In the process of interaction of neodymium oxide with neodecanoic acid is secreted significant amounts of water (to 1.5 mol per 1 mol of neodymium) and the concentration of hydrochloric acid in the course of the process varies considerably, which leads to a sharp decrease in the output of neodecanoate.

In the above method synthesized in accordance with this invention, neodecanoate neodymium used for the preparation of a homogeneous catalytic system consisting of three components: (a) neodecanoate neodymium) alkylamine or diisobutylaluminium and (C) organic halogen, preferably tert-butyl chloride, which was added to interact in hexane in the following order: B+a+C at a temperature of from 0 to 18°C. At the beginning and kept under stirring for 30 minutes, then added With enabling the mixture to react for another 30 minutes. Next, the catalyst was aged very early becauseā€- for 30 minutes before use in polymerization. The molar ratio between the components In and ranged from 5:1 to 50:1, and the molar ratio between C and And costal the lo from 0.2:1 to 4.5:1. The polymerization process carried out in solution continuously or intermittently at a temperature of from room temperature up to 150°C. the Obtained 1,4-CIS-polybutadiene contained 96-98,6% CIS-links. However, the conversion of monomer in this process is not high enough, which indicates insufficient high catalytic activity of the complex. In addition, the resulting polymer does not have complex properties (Mooney viscosity, molecular weight, polydispersity), optimal for the manufacture of elastomeric products.

The technical task of the present invention is to obtain (in metal reactors, for example, steel 12X18H10T) highly active catalytic component neodymium carboxylate and based catalytic complex to achieve in the process of (co)polymerization to high conversion of monomers to obtain (co)polymers of butadiene with a high content of 1,4-CIS-units, molecular weight and distribution of molecular weight, optimal for the manufacture of elastomeric products, especially for the automotive industry. This technical result is achieved by obtaining a catalytic component neodymium carboxylate for the polymerization of butadiene or copolymerization with isoprene interaction oxide neodymium neodecanoate acid in the presence of catalysts based on chlorine is Dov elements III, IV or VIII groups of the Periodic system or of zinc with aqueous solutions of pH 3-6,9, taken in an amount of 0.05 to 1.0 wt.% in relation to the original products and activators, forming with them a stable complexes. As catalysts for interaction oxide neodymium neodecanoate acid use neodymium chloride, aluminum chloride, zinc chloride, ferric chloride, Nickel chloride, silicon tetrachloride, etc. Activators, forming with the catalyst stable complexes, choose from a number of: esters, acetylacetone, chlorinated paraffin wax, water, hydrogen chloride, as well as trimethylphenylammonium chloride, N-methylpyridinium bromide, dimethyldodecylamine chloride etc. the Product of the interaction of oxide of neodymium with neodecanoic acid in the presence of catalysts, represent the solution neodecanoate neodymium

in organic solvents (hexane, cyclohexane or toluene)containing free neodecanoate acid and water at a ratio of 1:(0,33-1,39):(0,35-1,2).

Neodecanoate neodymium obtained by the above method, conforms to the technical specifications for neodecanoate neodymium TU - 2432-444-04872688-2002 on an experimental batch. Analysis of neodecanoate neodymium according to paragraph 4.2 THAT is produced by decomposition of a chemical compound of neodecanoate neodymium hydrochloric acid, separation of the degradation products is out by a titrimetric determination separately neodymium with Trilon B and neodecanoic acid and alkali. Determined the proportion of neodecanoate neodymium 0,85 g/cm3(at 25°C), melting point 68°C (at 760 mm Hg), molecular weight 657.

The interaction of the oxide with neodymium neodecanoate acid in the presence of metal salts can be carried out in mass or in solution, with the solvent used hydrocarbons, chlorinated paraffin wax, ketones, amines, esters, low doses of metal chloride and activator on the synthesis of neodecanoate leads to the low pH from 3 to 6.9). Therefore, the proposed method due to the low acidity of the reaction mixture allows the synthesis of neodecanoate neodymium in apparatus of stainless steel (for example, steel 12X18H10T), gives the ability to adjust the molar ratio neodecanoate neodymium: free neodecanoate acid: water, provides a high yield of the target product at the precise content of free neodecanoic acid. This method involves the application of 5-10 times smaller quantity of metal salt than mineral acids, therefore, the target product is clean, it does not form oily spots on the surface of the solution and insoluble resinous precipitation in the sludge. Use neodecanoic acid and the proposed method allows to process the unreacted products and completely eliminate thediplomat.

A new method of obtaining neodecanoate neodymium is characterized by purposeful introduction of micro-activating components selected from the group of esters, acetylacetone, chlorinated paraffin wax, water, hydrogen chloride, trimethylphenylammonium chloride, M-methylpyridinium bromide, dimethyldodecylamine chloride used in the synthesis of neodecanoate neodymium and allow not only to intensify the process of synthesis of the component, but also activate the catalytic complex, increase its stability during prolonged storage.

The technical result is also achieved by obtaining a catalytic system for the polymerization of butadiene or copolymerization with isoprene interaction of the catalytic component on the basis of neodecanoate neodymium with triisobutylaluminum and diisobutylaluminum, and the process is carried out by introducing into the hydrocarbon solution of butadiene, triisobutylaluminum, the catalytic component on the basis of neodecanoate neodymium, extract mixture and the introduction of diisobutylaluminium when the molar ratio of butadiene: triisobutylaluminum: neodecanoate neodymium: diisobutylaluminium (5-30):(2-10):1:(2-10), the catalytic component on the basis of neodecanoate neodymium use the above catalytic component, polycentricity way here.

As the halogenation agent is preferably used as a compound selected from the group stillunresolved, diisobutylaluminium, silicon tetrachloride, methyltrichlorosilane etc. at a molar ratio of halogenation agent: neodecanoate neodymium 1:(1,47-1,52).

When these ratios achieved the highest activity and stability during storage catalytic complex. For a long time retained catalytic activity.

In the preparation of the catalytic complex is the alkylation of neodymium and form an active polymerization.

The above technical result is also achieved by obtaining the (co)polymers of butadiene polymerization of butadiene or copolymerization with isoprene in solution in the presence of catalytic complex based neodecanoate neodymium, diisobutylaluminium and halogenation agent used for the above catalytic complex. The method involves different ratios of styrene:isoprene, but the best results are obtained by copolymerization mass ratio of styrene: isoprene (95-97):(5-3).

The produced copolymers of butadiene with isoprene, with a low content of isoprene, have high frost resistance, and rubber derived from them, low to the ratio of the abrasion. The resulting polymers are characterized by a narrow polydispersity, high content of 1,4-CIS-units, high output (co)polymer and the possibility of obtaining (co)polymers with predetermined molecular weight.

The essence of the present invention set forth in the following examples.

EXAMPLE 1.

In a metal beaker 150 ml download 0,0223 g setevogo aluminum chloride (0.05% of wt. in relation to the original product), 2,9 ml of 40%aqueous solution of diphenyloxide (DFO) in toluene, of 5.06 g of neodymium oxide and 19,6 g neodecanoic acid (pH of 3.0). The reaction mixture is heated with stirring to 70°C in a sand bath, then heated clean. Reaction mass boils, becomes transparent, its temperature rises to 117°C. After 40 minutes of cooling in the glass serves 60 ml of a mixture of cyclohexane with neprasam. After 30 minutes of sludge discharged 84 ml purple solution. The output neodecanoate neodymium 92,4% (wt.). The molar ratio of neodecanoic neodymium: free neodecanoate acid: water is 1:1,22:0,41.

EXAMPLE 2.

In a metal reactor with a capacity of 250 ml download 0,922 g setevogo aluminum chloride (0.9 percent compared to the original product), dissolved in 10 ml of water, 80 ml of hexane, 11,68 g of neodymium oxide. After stirring the mixture for 5 minutes, to the resulting suspension type 45 g neodecanoic acid (pH races is the thief of 3.6). Synthesis of lead 1.5 hours at a temperature of 55°C. After 30 minutes of sludge discharged 122 ml purple solution. The output neodecanoate neodymium 92% (wt.). The molar ratio of neodecanoic neodymium: free neodecanoate acid: water is 1:1,22:0,68.

EXAMPLE 3.

To increase the concentration of neodecanoate neodymium metal reactor with a capacity of 250 ml load 80 ml of the solution obtained according to example 2, a 2.01 g of neodymium oxide and 0,1124 g setevogo aluminum chloride (0,74% compared to the original products)dissolved in 5 ml of water (pH of 6.9). The synthesis is carried out at a stirring 1 hour at a temperature of 60°C. After 30 minutes of sludge discharged 80 ml. The output neodecanoate neodymium 95% (wt.). The molar ratio of neodecanoic neodymium: free neodecanoate acid: water is 1:0,78:1,08.

EXAMPLE 4

In a metal reactor with a capacity of 1 l load 23,36 g of neodymium oxide, 180 ml of a mixture of cyclohexane with neprasam, 83,01 g neodecanoic acid, 10 ml of 0.92 mol/l solution of silicon tetrachloride in a mixture of cyclohexane with neprasam, (1,4% compared to the original products) (0,33% wt. in relation to the original product) and 9 ml of 40% solution of the far Eastern Federal district. The synthesis is carried out at a stirring 2 hours at a temperature of 50°C. After 10 minutes of sludge discharged 290 ml. The output neodecanoate neodymium 100% (wt.). The molar ratio of neodecanoic neodymium: freedoms is th neodecanoate acid: water is 1:0,58:0,04.

EXAMPLE 5.

a) In a metal reactor with a capacity of 1 l pre-load sustained for 24 hours the mixture 0,726 g of zinc chloride (1.0% with respect to the original product), dissolved in 10 ml of water and 0.6 ml of 36% hydrochloric acid (pH of the aqueous phase at a 3.0). Then, the reactor serves 23,36 g of neodymium oxide, 180 ml of a mixture of cyclohexane with neprasam and 49,23 g neodecanoic acid. The synthesis is carried out at a stirring 1 hour at 85°C. After a 4-hour sludge discharged 245 ml purple solution. The molar ratio of neodecanoic neodymium: free neodecanoate acid: water is 1:0,49:1,22.

b) To improve the conversion of your source components to the water portion of the slurry obtained after separation of the hydrocarbon moiety in example 5A), which contained the 0,0259 mol of oxide of neodymium, 28 g of water, 0,0053 mol of zinc chloride (1.5% in comparison to the original product) and 0,0053 mol of hydrochloric acid was added 100 ml of a mixture of cyclohexane with neprasam and 28.5 g neodecanoic acid. The synthesis is carried out at a stirring 1 hour at a temperature of 85°C. After 3 hours of sludge discharged 134 ml purple solution. The output neodecanoate neodymium 94,6% (wt.). The molar ratio of neodecanoic neodymium: free neodecanoate acid: water is 1:0,55:0,81.

EXAMPLE 6.

In a metal reactor with a capacity of 250 ml download 0,4722 g of anhydrous ferric chloride (1.0% wt. in relation to the Ref who denim products), 11,05 g of neodymium oxide, 100 ml of chloroform and 36,17 g neodecanoic acid (pH of the aqueous phase of 5.0). The synthesis is carried out at a stirring 1.5 hours at a temperature of 60°C. After 40 minutes of sludge solution is separated from the sludge is transferred to a flask and distilled chloroform. The residue obtained after distillation of the chloroform, dissolved in 150 ml of hexane. Get 190 ml. The output neodecanoate neodymium 99% (wt.). The molar ratio of neodecanoic neodymium: free neodecanoate acid: water is 1:0,33:0,97.

EXAMPLE 7.

In a metal beaker 150 ml download 5.31g oxide of neodymium, 0,2259 g setevogo aluminum chloride (0.5 percent by weight. in relation to the original product), 0,1818 g of acetylacetone, 19,6035 g neodecanoic acid (pH of the aqueous phase 3.5), and 20 ml of a mixture of cyclohexane with neprasam. Synthesis is carried out for 1.5 hours at 55-70°C. After cooling, the content of glass add 90 ml of a mixture of cyclohexane with neprasam. After a 20 minute sludge discharged 132 ml of neodecanoate neodymium. The output neodecanoate neodymium 92% (wt.). The molar ratio of neodecanoic neodymium: free neodecanoate acid: water is 1:1,04:0,83.

EXAMPLE 8.

In a metal beaker 150 ml download 0,2068 g setevogo aluminum chloride (0,48% wt. in relation to the original product), dissolved in 5 ml of water, then add 0,1533 g trimethylphenylammonium chloride, dissolved the CSOs in 15 ml of ethanol. The mixture defend during the day. The solvent is then distilled off, get a paste catalyst light-brown color. Next, in a glass serving of 5.06 g of neodymium oxide and 18.9 g neodecanoic acid (pH of the aqueous phase 5). With stirring the reaction mass is heated to 58°is boiling for 1.5 minutes the temperature rises to 120°C. the Glass cooled, served him in 90 ml of a mixture of cyclohexane with neprasam. Unload 111 ml of neodecanoate neodymium. The output neodecanoate neodymium 99% (wt.). The molar ratio of neodecanoic neodymium: free neodecanoate acid: water is 1:0,80:0,35.

EXAMPLE 9.

In a metal beaker 150 ml download 0,2004 g setevogo aluminum chloride (0,44% wt. in relation to the original product), dissolved in 5 ml of water, 0,3487 g N methylpyridinium bromide dissolved in 15 ml of ethanol. The reaction mixture was incubated overnight, then the solvent is distilled off. In a glass add 5,3056 g of neodymium oxide, 15 ml of a mixture of cyclohexane with neprasam and 19,6 g neodecanoic acid (pH of the aqueous phase to 5.5). The synthesis is carried out at 50-68°C for 2 hours. To the resulting product, after cooling, add 90 ml of a mixture of cyclohexane with neprasam. Unload 108 ml neodecanoate neodymium. The output neodecanoate neodymium 87.2% (wt.). The molar ratio of neodecanoic neodymium: free neodecanoate islote: water is 1:1,27:0,96.

EXAMPLE 10.

In a metal beaker 150 ml download 0,2004 g setevogo aluminum chloride (0.44 per cent in relation to the original substances), dissolved in 5 ml of water, 0,2633 g dimethyldodecylamine chloride, dissolved in 15 ml of ethanol. The mixture was kept during the day. The solvent is then distilled off, add 5,3073 g of neodymium oxide, 15 ml of a mixture of cyclohexane with neprasam and 19,6087 g neodecanoic acid (pH of the aqueous phase of 6.0). With stirring the reaction mass is heated to 55°With, then within 5 minutes the temperature spontaneously rises to 85°C. the Reaction is carried out for 1 hour, then the reaction mass is then cooled and add 90 ml of a mixture of cyclohexane with neprasam. Unload 118 ml solution neodecanoate neodymium. The output neodecanoate neodymium 84.7% (wt.). The molar ratio of neodecanoic neodymium: free neodecanoate acid: water is 1:1,39:1,05.

EXAMPLE 11.

In a metal beaker 150 ml download 5,3038 oxide of neodymium, 0,3031 g setevogo neodymium chloride (0,85% wt. in relation to the original product), 2,9 ml of 40%solution of diphenyloxide in toluene, 19,6017 g neodecanoic acid and 15 ml of a mixture of cyclohexane with neprasam (pH of the aqueous phase of 5.1). Synthesis is carried out for 1 hour under stirring and the temperature 52-65°C. Then cooled to product add 90 ml of a mixture of cyclohexane from nefra the om. After 50 minutes of sludge discharged 109 ml. The output neodecanoate neodymium 92% (wt.) The molar ratio of neodecanoic neodymium: free neodecanoate acid: water is 1:1,05:0,96.

EXAMPLE 12.

In a metal beaker 150 ml download 5,3091 oxide of neodymium, 0,3444 g setevogo neodymium chloride (0,88% compared to the original product), 0,2889 g of acetylacetone 19,6017 g neodecanoic acid and 15 ml of a mixture of cyclohexane with neprasam. Synthesis is carried out for 1 hour under stirring and the temperature of 55-60°C. After cooling, to the resulting product add 90 ml of a mixture of cyclohexane with neprasam (pH of the aqueous phase to 3.2). After a 50-minute sludge discharged 112 ml. The output neodecanoate neodymium 94,3% (wt.). The molar ratio of neodecanoic neodymium: free neodecanoate acid: water is 1:0.95 to: 1,05.

EXAMPLE 13 (comparative).

In a glass flask with a capacity of 1 l with agitator load 120 ml (78,16 g) hexane and 23,36 g of neodymium oxide containing 81,75% neodymium. With vigorous stirring, add 2 ml of 36%hydrochloric acid (0,84% compared to the original product), diluted in 10 ml of water (pH of the solution of 0.32), of 78.47 g neodecanoic acid. The synthesis is carried out at a temperature of 55°C for 1 hour. After a 12-hour sludge discharged 214 ml of neodecanoate neodymium containing 8,29% (wt.) neodymium, 16,15% (wt.) free neodecanoato the acid and 0.82% (wt.) water. The output neodecanoate neodymium 73,5% (wt). The molar ratio of neodecanoic neodymium: free neodecanoate acid: water is 1: 1,68: 1,45.

EXAMPLE 14.

In Tryokhgornaya flask with a capacity of 250 ml, equipped with a magnetic stirrer, inert gas-argon, download 46,0 mmol of butadiene-1,3, dissolved in 75 ml of a mixture of cyclohexane with neprasam, 7 ml of 1.1 mol/l solution of triisobutylaluminum (CHIBA) and 4,0687 g of the solution of neodecanoate neodymium obtained in example 1 (1.54 mmol). The reaction mixture was incubated for 42 hours at a temperature of 20°C. Then it was added 3 ml, 1.01 mol/l solution of diisobutylaluminium (DIBAH), stirred for 30 minutes and add 11 ml of 0.07 mol/l solution of ethylaminoethanol (EACH) 2,31 mmol (chlorine). The obtained catalytic complex used in the polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG: [CL] is 30:5:1:2:1,5.

EXAMPLE 15.

In the flask, as in example 14, the load of 7.7 mmol of butadiene-1,3, dissolved in 65 ml of a mixture of cyclohexane with neprasam, 7 ml of 1.1 mol/l solution CHIBA and 4,0155 g of the solution of neodecanoate neodymium (of 1.52 mmol)obtained in example 1. The mixture was incubated for 96 hours at a temperature of 20°then it was added to 3.1 ml, 1.01 mol/l solution DEBUG, stirred for 30 minutes and served in apparatus for polymerization, in which simultaneously load 11 ml of 0.07 Mall solution EACH in number (2,31 on chlorine mmol). The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG: [CL] is 5,06:5,06:1:2,05:1,52.

EXAMPLE 16.

In the flask, as in example 14, the load 15 mmol of butadiene-1,3, dissolved in 40 ml of a mixture of cyclohexane with neprasam, and 7.1 ml of 1.1 mol/l solution CHIBA and 2,6977 g of the solution of neodecanoate neodymium (1.5 mmol)obtained in example 2. The mixture is kept for 19 hours at a temperature of 20°and add 3 ml, 1.01 mol/l solution DIBAG. After 15 minutes of mixing the catalytic complex used for polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG is 10:5,0:1:2.

EXAMPLE 17.

In the flask, as in example 14, load 7.8 mmol of butadiene-1,3, dissolved in 70 ml of a mixture of cyclohexane with neprasam, 6.9 ml of 1.1 mol/l solution CHIBA and 2,2584 g of the solution of neodecanoate neodymium (1.5 mmol)obtained in example 3. The reaction mixture was stirred for 1.5 hours at a temperature of 50°and add 3 ml, 1.01 mol/l solution DIBAG. After 5 minutes of mixing the catalytic complex used for polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG is 5,2:5,0:1:2,0.

EXAMPLE 18.

In the flask, as in example 14, the load of 7.6 mmol of butadiene-1,3, dissolved in 50 ml of a mixture of cyclohexane with neprasam, 6.9 ml of 1.1 mol/l solution CHIBA and 2,9042 g of the solution of neodecanoate neodymium (1.5 mmol)obtained in the example is 4. Reaction to withstand the weight 19 hours at a temperature of 20°and add it to 2.9 ml, 1.01 mol/l solution DIBAG. After 5 minutes of mixing the catalytic complex used for polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG is 5:5:1:2.

EXAMPLE 19.

In the flask, as in example 14, the load of 11.4 mmol of butadiene-1,3, dissolved in 50 ml of a mixture of cyclohexane with neprasam, 6.9 ml of 1.1 mol/l solution CHIBA and 3,4848 g of the solution of neodecanoate neodymium (1,51 mmol)obtained in example 56). The reaction mixture is kept for 16 hours at a temperature of 20°and add 3 ml, 1.01 mol/l solution DIBAG. After stirring for 20 minutes catalytic complex used for polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG 7.5:5:1:2.

EXAMPLE 20.

In the flask, as in example 14, download EUR 7.57 mmol of butadiene-1,3, dissolved in 45 ml of a mixture of cyclohexane with neprasam with 2.7 ml of 1.1 mol/l solution CHIBA and 3,4897 g of the solution of neodecanoate neodymium (1.5 mmol)obtained in example 6. The reaction mixture is kept for 72 hours at a temperature of 20°and added to 2.8 ml, 1.01 mol/l solution DIBAG. After 5 minutes of mixing the catalytic complex used for polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG is 5.0:2:1:2.

EXAMPLE 21.

In the flask, as is the example 14, download EUR 7.57 mmol of butadiene-1,3, dissolved in 45 ml of a mixture of cyclohexane with neprasam, of 13.7 ml of 1.1 mol/l solution CHIBA and 4,2706 g of the solution of neodecanoate neodymium (1,51 mmol)obtained in example 7. The reaction mixture was kept for 15 minutes at a temperature of 50°and add 3 ml, 1.01 mol/l solution DIBAG. After 15 minutes of mixing the catalytic complex used for polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG is 5:10:1:2.

EXAMPLE 22.

In the flask, as in example 14, load 7.9 mmol of butadiene-1,3, dissolved in 40 ml of a mixture of cyclohexane with neprasam, 14,5 ml of 1.1 mol/l solution CHIBA and 4,5797 g of the solution of neodecanoate neodymium (1,578 mmol)obtained in example 8. The reaction mixture is kept for 19 hours at a temperature of 22°and type of 3.1 ml, 1.01 mol/l solution DIBAG. After 30 minutes of mixing the catalytic complex used for polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG is 5:10:1:2.

EXAMPLE 23.

In the flask, as in example 14, load 7.8 mmol of butadiene-1,3, dissolved in 40 ml of a mixture of cyclohexane with neprasam, 4,1 ml of 1.1 mol/l solution CHIBA and 4,3995 g of the solution of neodecanoate neodymium (1,522 mmol)obtained in example 9. The reaction mixture was incubated for 36 hours at a temperature of 20°and add 3 ml, 1.01 mol/l solution DIBAG. After a 15-minute displaced the air traffic management the catalytic complex used for polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG is 5:3:1:2.

EXAMPLE 24.

In the flask, as in example 14, load 7.8 mmol of butadiene-1,3, dissolved in 40 ml of a mixture of cyclohexane with neprasam, 6.2 ml of 1.1 mol/l solution CHIBA and 4,9983 g of the solution of neodecanoate neodymium (1,542 mmol)obtained in example 10. The reaction mixture is kept for 17 hours at a temperature of 20°and added to 2.7 ml, 1.01 mol/l solution DIBAG. After 15 minutes of mixing the catalytic complex used for polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG is 5.0:4,4:1:2.

EXAMPLE 25.

In the flask, as in example 14, the load of 7.68 mmol of butadiene-1,3, dissolved in 75 ml of a mixture of cyclohexane with neprasam, 6.9 ml of 1.1 mol/l solution DEBUG and 3,3236 g of the solution of neodecanoate neodymium (1.53 mmol)obtained in example 11. After stirring the reaction mixture for 20 minutes at a temperature of 40°With the use of a catalytic system for polymerization.

EXAMPLE 26.

In the flask, as in example 14, the load of 7.68 mmol of butadiene-1,3, dissolved in 75 ml of a mixture of cyclohexane with neprasam and 7.6 ml of 1.1 mol/l solution DEBUG and 3,0651 g of the solution of neodecanoate neodymium (1.53 mmol)obtained in example 12. The reaction mixture was kept for 15 minutes at a temperature of 50°and use of a catalytic system for polymerization. Mole of zootoxin the e butadiene: CHIBA: neodecanoate neodymium: DEBUG is 5:2:1:10.

EXAMPLE 27.

In the flask, as in example 14, load 7.8 mmol of butadiene-1,3, dissolved in 40 ml of a mixture of cyclohexane with neprasam, 6.2 ml of 1.1 mol/l solution CHIBA and 5,0287 g of the solution of neodecanoate neodymium (1,551 mmol)obtained in example 10. The reaction mixture is kept for 17 hours at a temperature of 20°and added to 2.8 ml, 1.01 mol/l solution DIBAG. After 15 minutes of mixing the catalytic complex used for polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG is 5:4,4:1:2.

EXAMPLE 28.

In the flask, as in example 14, download 15.8 mmol of butadiene-1,3, dissolved in 70 ml of a mixture of cyclohexane with neprasam, 8,3 ml of 1.1 mol/l solution CHIBA and 3,0021 g of the solution of neodecanoate neodymium (1.55 mmol)obtained in example 4. The reaction mixture is kept for 19 hours at a temperature of 20°and type of 3.1 ml, 1.01 mol/l solution DIBAG. After 15 minutes of mixing the catalytic complex used for polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG is 10.2:5,9:1:2.

EXAMPLE 29 (comparative).

In Tryokhgornaya flask with a capacity of 250 ml, equipped with a magnetic stirrer, inert gas-argon (nitrogen) load of 7.7 mmol of butadiene-1,3, dissolved in 65 ml of a mixture of cyclohexane with neprasam, 7 ml of 1.1 mol/l solution CHIBA and 2,6789 g (1.54 mmol) of a solution of neodecanoate neodymium poluchennogo example 13. The reaction mixture is cooled to 10°C, kept at this temperature and stirred for 30 minutes and add to it and 23.1 ml of 0.1 mol/l solution of tributylamine in hexane. The mixture was incubated for 48 hours at a temperature of 10°C. Then added 3.1 ml of 1.01 mol/l solution DEBUG, stirred for 20 minutes and use in polymerization. The molar ratio of butadiene: CHIBA: neodecanoate neodymium: DEBUG is 5:5:1:1,5:2.

EXAMPLE 30.

In the apparatus load 1095 g of butadiene-1,3, dissolved 8.4 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 14, 6.8 ml 1.01 mol/l solution DEBUG and conduct the polymerization for 3 hours at a temperature of 55-60°With, the final conversion of 89% (wt). Contents 1-CIS links to 98%, a polydispersity of 3.14. The molar ratio of DEBUG: neodecanoato neodymium is 1:45.

EXAMPLE 31.

In the apparatus load 1095 g of butadiene-1,3, dissolved 8.4 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 15, 6 ml, 1.01 mol/l solution DEBUG and conduct the polymerization for 3 hours at a temperature of 55-60°With, the final conversion of 91% (wt). Contents 1-CIS links - of 97.6%, a polydispersity 3,24. The molar ratio of DEBUG: neodecanoato neodymium is 1:4.

EXAMPLE 32.

the apparatus upload 1090 g of butadiene-1,3, dissolved in 8.5 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 16, 6.9 ml 1.01 mol/l solution DEBUG and 45 ml of 0.05 mol/l solution of EACH. The total reaction time at a temperature of 55-60°3 hours; the final conversion of 96% (wt). Contents 1-CIS links of 98.2%, a polydispersity - 2,84. The molar ratio of DEBUG: neodecanoato neodymium: EACH is 1:4,6:1,5.

EXAMPLE 33.

In the apparatus upload 1090 g of butadiene-1,3, dissolved in 8.5 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 17, 7 ml, 1.01 mol/l solution DEBUG and 10.5 ml of 0.07 mol/l solution of EACH. The total reaction time at a temperature of 55-60°3 hours; the final conversion of 94% (wt). Contents 1-4 CIS links - of 98.2%, a polydispersity-2.91 in. The molar ratio of DEBUG: neodecanoato neodymium: [CL] 1:4,7:1,5.

EXAMPLE 34.

In the apparatus load 1044 g of butadiene-1,3, dissolved in 8.2 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 18, 7 ml, 1.01 mol/l solution DEBUG and 22.5 ml of 0.1 mol/l diisobutylaluminium (DIBAH). The polymerization are 3 hours at a temperature of 55-60°; final conversion of 97% (wt). Contents 1-4 CIS links -98,2%, a polydispersity 2,84. The molar ratio of DEBUG: neodecanoato ambiguity of the mA: [CL] 1:4,7:1,5.

EXAMPLE 35.

In the apparatus upload 1090 g of butadiene-1,3, dissolved in 8.5 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 19, 6.8 ml 1.01 mol/l solution DEBUG and 22.5 ml of 0.1 mol/l DIBAH. The polymerization are 3 hours at a temperature of 55-60°; final conversion of 86% (wt). Contents 1-4 CIS links - 97% (wt.), the polydispersity -3,27. The molar ratio of DEBUG: neodecanoato neodymium: [CL] 1:4,5:1,49.

EXAMPLE 36.

In the apparatus load 1044 g of butadiene-1,3, dissolved in 8,1 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 20, 7,4 ml, 1.01 mol/l solution DEBUG and 22 ml of 0.1 mol/l DIBAH. The polymerization are 3 hours at a temperature of 55-60°; end-conversion of 90% (wt). The content of 1,4 - CIS units to 96.5%, a polydispersity of 2.58. The molar ratio of DEBUG: neodecanoato neodymium: [CL] 1:5:1,47.

EXAMPLE 37.

In the apparatus load 1038 grams of butadiene-1,3, dissolved in 8.6 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 21, 7,5 ml, 1.01 mol/l solution DEBUG and 11 ml of 0.05 mol/l of silicon tetrachloride. The total polymerization time of 3 hours at a temperature of 55-60°; final conversion of 85% (wt). Contents 1-4 CIS links to 96.9%, a polydispersity of 3.05. Mole of cootes is of DEBUG: neodecanoato neodymium: [CL] 1:5:1,47.

EXAMPLE 38.

In the apparatus load 1128 grams of butadiene-1,3, dissolved in 8.6 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 22, 7 ml, 1.01 mol/l solution DEBUG and 29 ml of 0.04 mol/l of ethylaminoethanol. The polymerization are 3 hours at a temperature of 55-60°; final conversion of 93% (wt). Contents 1-4 CIS links - 97% (wt.), the polydispersity - 2,96. The molar ratio of DEBUG: neodecanoato neodymium: [CL] 1:4,48:1,47.

EXAMPLE 39.

In the apparatus upload 1090 g of butadiene-1,3, dissolved in 8.5 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 23, and 6.6 ml, 1.01 mol/l solution DEBUG and 22.8 ml of 0.1 mol/l trimethylchlorosilane. The total reaction time of 3 hours at a temperature of 55-60°; end-conversion of 90% (wt). Contents 1-4 CIS links to 98% (wt.), the polydispersity - 2,82. The molar ratio of DEBUG: neodecanoato neodymium: [CL] 1:4,4:1,5.

EXAMPLE 40.

In the apparatus upload 1090 g of butadiene-1,3, dissolved in 8.5 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 24, 7,0 ml, 1.01 mol/l solution DEBUG and 11 ml of 0.07 mol/l solution of ethylaminoethanol. The total reaction time of 3 hours at a temperature of 55-60°; final conversion of 91% (wt). Contents 1-4 CIS links -979% (wt.), the polydispersity - 2,87. The molar ratio of DEBUG: neodecanoato neodymium: [CL] 1:4,6:1,51.

EXAMPLE 41.

In the apparatus load 1095 g of butadiene-1,3, dissolved 8.4 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 25, with 7.6 ml, 1.01 mol/l solution DEBUG and 7.6 ml of 0.1 mol/l solution of methyltrichlorosilane. The total reaction time of 3 hours at a temperature of 55-60°; end-conversion of 90% (wt). The content of CIS-links in the polymer -97,5%, a polydispersity 2,88. The molar ratio of DEBUG: neodecanoato neodymium: [CL] 1:5:1,49.

EXAMPLE 42.

In the apparatus load 1095 g of butadiene-1,3, dissolved 8.4 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 26, 7,2 ml, 1.01 mol/l solution DEBUG and 11 ml of 0.07 mol/l solution of ethylaminoethanol. The polymerization are 3 hours at a temperature of 55-60°; final conversion of 94% (wt). Zderzenie 1-4 CIS links to 95%, a polydispersity of 2.81. The molar ratio of DEBUG: neodecanoato neodymium: [CL] 1:4,75:1,51.

EXAMPLE 43.

In the apparatus load 1045 g of butadiene-1,3 and 55 grams of isoprene dissolved in 8.4 litre of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 27, to 7.9 ml, 1.01 mol/l solution DEBUG and 23 ml of 0.1 mol/l diisobutylaluminium (ON THE BACH). The polymerization are 3 hours at a temperature of 55-60°; final conversion of 95% (wt). The content of 1,4-CIS units -97,2% (wt.), the polydispersity - 2.91 in. The molar ratio of DEBUG: neodecanoato neodymium:[CL] 1:5,1:1,49.

EXAMPLE 44.

In the apparatus load 1060 g of butadiene-1,3 and 33 grams of isoprene dissolved in 8.4 litre of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 28, to 7.9 ml, 1.01 mol/l solution DEBUG and 23 ml of 0.1 mol/l solution of diisobutylaluminium (DIBAH). The polymerization are 3 hours at a temperature of 55-60°; final conversion of 94% (may). The content of 1,4-CIS units with 97.1%, a polydispersity of 3.0. The molar ratio of DEBUG: neodecanoato neodymium: [CL] 1:5,1:1,49

EXAMPLE 45 (comparative).

In the apparatus upload 1090 g of butadiene-1,3, dissolved 8.4 l of a mixture of cyclohexane with neprasam, heated to a temperature of 40°add catalytic complex obtained in example 29, 7,2 ml, 1.01 mol/l solution DIBAG. The polymerization is conducted for 3 hours at a temperature of 55-60°; end conversion 60,7% (wt). The content of CIS-links in the polymer of 98.2% (wt.), the polydispersity - 3,42. The molar ratio of DEBUG: neodecanoato neodymium: [CL] 1:4,7:1,5.

The table presents the synthesis conditions and properties of samples of polybutadiene and copolymers of butadiene with isoprene, obtained in accordance with pridlagayetsya. The examples described above and the results presented in the table indicate that the proposed method of synthesis catalytic component, the formation based homogeneous catalytic complex and the use for the polymerization of butadiene-1,3 and its copolymerization with isoprene allows to obtain (co) polymers of a given quality at a high conversion of monomers.

1. The method of obtaining a catalytic component for polymerization of butadiene or copolymerization with isoprene direct catalytic interaction of neodymium oxide with neodecanoic acid, characterized in that the interaction between the oxide of neodymium and neodecanoic acid is carried out in the presence of a catalyst selected from the group consisting of chlorides of elements of the III, IV or VIII groups of the Periodic system, or zinc, having a pH of aqueous 3-6,9, taken in an amount of 0.05 to 1.0 wt.% in relation to the original product, and activators, forming with them a stable complexes.

2. The method according to claim 1, characterized in that the catalysts of the interaction of oxide of neodymium with neodecanoic acid use chlorides selected from the group of neodymium chloride, zinc chloride, aluminum chloride, ferric chloride, silicon tetrachloride.

3. The method according to claim 1, characterized in that as activator is, forming a catalyst sustainable use complexes, compounds selected from a number of esters, acetylacetone, chlorinated paraffin wax.

4. Catalytic component for the polymerization of butadiene copolymerized with isoprene, which is a product of the interaction of oxides of neodymium and neodecanoic acid, characterized in that it is obtained by the method according to claims 1 to 3.

5. The method for the catalytic system for the polymerization of butadiene or copolymerization with isoprene interaction catalytic component with alyuminiiorganicheskikh connection, wherein the process is carried out by introducing into the hydrocarbon solution of butadiene, triisobutylaluminum, the catalytic component on the basis of neodecanoate neodymium, aging the resulting mixture for 15 min to 96 hours at a temperature of 20-50°followed by the introduction of diisobutylaluminium when the molar ratio of butadiene:triisobutylaluminum: catalytic component:diisobutylaluminium (5-30):(2-10):1:(2-10), use of the catalytic component on the basis of neodecanoate neodymium obtained according to claim 4.

6. The method according to claim 5, characterized in that impose additional halogenation agent at a molar ratio neodecanoate neodymium:halogenation agent 1:(1,47-1,52).

7. Catalytic system for the polymerization of butadiene or copolymerization E. what about with isoprene, representing the product of the interaction of the catalytic component on the basis of neodecanoate neodymium with alyuminiiorganicheskikh connection, characterized in that it is obtained by the method according to claim 5.

8. The method of obtaining the (co)polymers of butadiene polymerization of butadiene or copolymerization with isoprene in solution in the presence of a catalytic complex comprising a catalytic component and alyuminiiorganicheskikh connection, characterized in that the catalytic complex used catalytic complex according to claim 7.

9. The method according to claim 7, characterized in that the process is carried out in the presence of a halogenation agent is a compound selected from the group ethylaminoethanol, diisobutylaluminium, silicon tetrachloride, METHYLCHLOROSILANE.

10. The method according to claim 7, characterized in that the mass ratio of styrene:isoprene is (95-97):(5-3).

11. (Co)polymer of butadiene obtained by the method according to claims 7 and 9.



 

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