TH32091B - Polybutadiene production process - Google Patents

Abstract

DC60 (21/06/53) Polybutadiene sis-1,4-High was produced with a gel reduction, by preparing a catalyst from (A) cobalt compound, (B). ) Trialkyl compound (C1-10) aluminum, (C) halide compound Choose from formulas (1) and (2) AlR2 mX3-m (1), R3-X(2), where R2 = C1-10 hydrocarbons, X = halogens, m = 0-2, R3 = C1-40 hydrocarbons and (D) water in the amount of 0.77-1.45 mol/mol of total A1 in substance (B) and (C) and polymerization 1,3-butadiene with the resulting accelerators in the polymerization medium including alkanes, cycloalkanes or olefin hydrocarbons, polybutadiene sis-1,4- was produced at high volumes. with the reduction of gelling, by preparing the accelerator from (A) cobalt compound. (B),Trialkyl Compound (C1-10) Aluminum (C) Halide Compound Choose from formulas (1) and (2): ALR2 mX3-m (1), R3-X( 2), where R2 = C1-10 hydrocarbons, X = halogens, m = 0-2, R3 = C1-40 hydrocarbons and (D) water in the amount of 0.77-1.45 mol/mol of total AL in the substance ( B) and (C) and polymerization 1,3-butadiene. The resulting accelerators in the polymerization medium include alkanes, cycloalkanes or olefin hydrocarbons:

Claims (9)

1.Polybutadiene production process The structural content of cyst 1,4 95% or more consisted of accelerated preparations from (A) cobalt containing At least one selected cobalt compound from colobalt halite, cobalt salt of organic and inorganic acids, cobalt acetylacetonate, cobalt complex. Acetate, cobalt complex Halides-pyridine, cobalt complex, cobalt complex Halides-picoline, and cobalt-halide-alkyl-alkyl complexes (B), an organic aluminum compound containing at least one tri-alkylolic compound The minum follows the formula (1) (R1) 3Al (1) where R1 represents the alkyl group containing 1-10 carbon atoms, in which the alkyl group may be replaced (C). At least one member chooses from a group containing (a) the aluminum halide compound according to the formula (2) AIR2mX3 .. (2) where R2 represents the hydrocarbon group having 1-10 carbon atoms, whose hydrocarbon group may be replaced X. For halogen atoms, m for positive numbers 0-2, (b) halite hydrocarbon compounds according to formula (3); R3-X (3), where X is the above, and R3 represents 1-40 hydrocarbon groups. The carbon atoms in which the hydrocarbon group may be replaced, and (D) water in the amount of 0.77-1.45 mol per mole of all the aluminum in substances (B) and (C) and polymers 1,3. - Butadiene The accelerator is also present. 2. Process according to claim 1. Cobalt (A) is available in quantities of 1x10 -7 to 1x10 -4 mil per mole of 1,3-butadiene. 3. Process according to claim No. 1 Organic alumina (B) appears in amounts of 10-5000 mol per mole of cobalt (A) 4. Process according to claim No. 1 by the atomic (X / Al) ratio of all halogen atoms in the alite (C) to all aluminum atoms The organic aluminum (B) and the halide (C) are in the range 0.02-1.33 5. The process of claim No. 4 Halide (C) will include at least one alu compound. Minumhalides (2) and the atomic ratio (X / Al) of all halogen atoms in the alite (C) to all alumina atoms in the aluminate. Organic (B) and halide (C) ranges from 0.01-0.9 6. Process according to claim 1: accelerated preparation by mixing substances (A), (B), (C) and (D) in Any order. 7. Process according to claim 6: organic alumina (B) mixed with halide (C), resulting mixture (B + C) mixed with water (D) and Mixture (B + C + D) that was mixed with cobalt (A) 8. Process according to claim 6: Organic aluminum (B) cured with halide (C) at temperature. -50 to 80 C for 0.1-24 h. Curing product is mixed with cobalt (A) and water (D) in any order. 9. Process according to claim No. 1, where in the preparation of accelerator Organic aluminum (B) contains at least one tri-alkyl aluminum. In which each alkyl group has 1-10 carbon atoms, the halide (C) will have at least one organic aluminum halide according to the formula (2 \ ') ALR2 pX3-P (2 \'). Where X is as above, R2 is defined above and P represents 1-2, and the atomic ratio (X / Al) of all halogen atoms in halide (C) to alumi atoms. All aluminum In organic aluminum (B) and halides (C) in the range 0.1-0.9 1 0. Process according to claim No. 1, in the preparation of accelerators, organic alumides ( B) It reacts with water first (D) to obtain alumoxane (BD), which contains at least one alumoxane, re-distributed according to the formula R1 (Al-O) n-, where R1 is as follows. Given above, n represents an integer 1 or more, the resulting alumoxane (BD) is mixed with cobalt (A) and halide (C) in any order 1. 1. Process according to claim No. 10. In the preparation of alumoxane accelerator (BD), it was mixed with halide (C) at temperature -50 to 80 C for 0.1-10 hours and then Cured product mixed with cobalt (A) 1 2. Process according to claim 11 by preparing an additional accelerator, organic aluminum (E) available. At least one tri-alkyluminum compound according to formula (4) (R4) 3Al (4) with R4 representing 1-10 alkyl group carbon atoms, added to the cobalt ( A) Aluoxane (BD) and halide (C) 1 3. Process according to claim 12, in which the preparation of accelerator, alumoxane (BD) and halide (C) is incubated with organic alumoxane (E). At temperatures -50 to 80 C. For 0.1-10 hrs. And then the product Cured and mixed with cobalt (A) 1 4. Process according to claim No. 10 by alumoxane (BD) contains 10-5000 mol per mol of cobalt (A) 1. 5. Process according to claim No. 10 with the atomic ratio (X / AL) of all halogen atoms in halide (C) to all alumina atoms. In alumoxane (BD) and halide (C) in the range 0.02-1.33 1 6. Process according to claim 123, with the atomic ratio (X / AL) of all halogen atoms in halide (C) to all aluminum atoms. In the alumoxane (BD), the halide (C) and the additional organic alumina (E) in the range 0.02-2.0 1. 7. Process according to claim No. 1 by polymerization of 1,3-butadiene Will be done in the medium Polymers, consisting of one or more substances selected from the group containing saturated aliphatic hyocarbons, cycloalipatic hydrocarbons (cycloalkanes), and aliphatic hydrocarbons. Saturated ethylene 1 8. The process of claim No. 17 by the polymerization medium consists of at least one member selected from a group consisting of: n-hexane, n-butane, n-heptane, n-pentane, cyclopentane, cyclohexane, 1-butene, cyste- 2-butene, and trans-2-butene 1 9. The production process of polybutadiene with a structural content of cyst -1,4 95% or more consists of 1,3-butadiene polymerization with catalysts. with The accelerator is obtained from (A) cobalt compounds containing at least one cobalt-selective compound from cobalt halides, cobalt salts of organic and inorganic acids, cobalt-a compounds. Cetyl acetonate, cobalt-acetate ester complex, cobalt halite-pyridine complex, cobalt halide pico complex Lean, and cobalt halide-alkyl alcohol complexes (B), organic alumines containing at least one triacyluminum compound according to the formula. (1) (R1) 3 Al (1) where R1 represents an alkyl group containing 1-10 carbon atoms to which the alkyl group may be replaced (C) a halide containing at least one of the selected members. From the group containing (a) the aluminum halide compound according to formula (2) (A1R2 mX3-1 (2), R2 represents the hydrocarbon group with 1-10 carbon atoms. Where the hydrocarbon group may be replaced, X for the halogen atom, and m for the positive number 0.2 and (b) halide hydrocarbon compounds according to the formula (3) R3-X (3), where X is as above and R3. Replace hydrocarbon groups with 1-40 carbon atoms in which the hydrocarbon group is replaced and (D) water in the amount of 0.77 to 1.45 mol per ml of total aluminum in substances (B) and (C).