RU2345092C1 - Method of obtaining catalyst of butadiene polymerisation and co-polymerisation of butadiene with isoprene - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining catalyst of butadiene polymerisation and co-polymerisation of butadiene with isoprene. Described is method of obtaining catalyst of butadiene polymerisation and co-polymerisation of butadiene with isoprene by interaction of components, which include rare-earth metal compound, conjugated diene and trialkylaluminium, standing of reaction mass and further introduction of diisobutylaluminium hydride and alkylaluminium halogenide, rare-earth compound and conjugated diene, as such piperylene is used, are supplied into trialkylaluminium and process is carried out with molar ratio trialkylaluminium: rare-earth metal compound: piperylene: diisobutylaluminium hydride: alkylaluminium halogenide (by Cl), equal 6÷12:1:1÷20:6÷12:1.8÷3.

EFFECT: increase of catalyst activity.

1 cl, 5 ex

Description

The invention relates to methods for producing a polymerization catalyst for butadiene and copolymerization of butadiene with isoprene and may find application in the synthetic rubber industry in the production of cis-1,4-polydienes.

A known method of producing a catalyst for the polymerization of butadiene and its copolymerization with isoprene by reacting a carboxylate compound of a rare-earth element (REE) with a halide-containing organoaluminum compound, diisobutylaluminum hydride (DIBAG) and triisobutylaluminum (TIBA) in the presence of 1 piperylene at 1: : (3.75 ÷ 11.75) :( 3.75 ÷ 11.25): 10 (US Pat. RF 2087488, C08F 136/06, prior dated 16.03.94). A solution of REE carboxylate, piperylene, DIBAG and TIBA solutions are successively added to the toluene solution of alkylaluminium halide, after which a catalyst is used for (co) polymerization in toluene or hexane at 50 ° C.

However, the resulting catalyst has a low activity: the polymer yield for 1 hour is not more than 53%.

A known method of producing a catalyst for the polymerization of butadiene and copolymerization of butadiene with conjugated dienes, in particular isoprene, which consists in the preliminary interaction of neodymium or didyme carboxylate, conjugated diene (piperylene or isoprene) and DIBAG, keeping the mixture for 10-30 minutes, and then introducing TIBA and alkylaluminium halide (US Pat. RF 2267497, C08F 4/52, prior. 12/22/2003). The molar ratio of REE: DIBAG: TIBA: alkylaluminium halide (according to Cl): conjugated diene is 1: 3 ÷ 12: 6 ÷ 12: 1,5 ÷ 3: 2 ÷ 20. Despite the increased activity of the catalyst, the yield of the (co) polymer of butadiene obtained using it, within 30 minutes, ranges from 65-87%. In addition, the method has a significant drawback, which consists in strict time limits for the interaction of REE compounds, conjugated diene and DIBAG - 10–30 minutes, which significantly complicates the control of the process on an industrial scale, since even a slight increase or decrease in reaction time, according to the authors of this application, leads to a decrease in the activity of the catalytic system, a change in the molecular characteristics of the polymers and the associated instability of properties.

Closest to the proposed technical solution, the technical essence is a method of producing a catalytic complex for the polymerization of butadiene or its copolymerization with isoprene by introducing TIBA butadiene and a specially synthesized catalytic component based on Nd neodecanoate into a hydrocarbon solution by holding the mixture for 15 minutes to 96 hours at 20-50 ° C followed by the introduction of DIBAG and a halogenating agent. Moreover, as follows from the description of the patent, a halogenated compound, as a rule, is already added to the monomer solution after the catalytic complex is fed. In this case, an additional amount of DIBAG is necessarily introduced into the monomer solution.

The molar ratio of butadiene: TIBA: neodecanoate: DIBAG: halogen is (5 ÷ 30) :( 2 ÷ 10): 1: (2 ÷ 10) :( 1.47 ÷ 1.52), respectively.

The catalytic component is synthesized by reacting neodymium oxide with neodecanoic acid in the presence of a catalyst selected from the group containing chlorides of elements of the III, IV, VIII groups of the periodic system or zinc, having a pH of aqueous solutions of 3.6 ÷ 3.9, taken in an amount of 0.05 ÷ 1.0 wt.% Of the starting products and activators forming stable complexes with them, selected from the group of esters, acetylacetone or chloroparaffins. (RF patent 2248845, B01J 37/04, C08F 4/52, prior. 04/29/2004).

However, according to the patent given in Examples 30-44 and describing the (co) polymerization of butadiene, the activity of the catalytic complex is small, since monomer conversion of 85 ÷ 97% is achieved only in 3 hours. And during (co) polymerization in the presence of a fully preformed catalytic complex, the degree of conversion of the monomer to the polymer is 89–91% (Examples 14/30 and 15/31). According to the authors of this application, this corresponds to a polymer yield in 3 hours of 85 ÷ 97%, however, in 1 hour the polymer yield ranges from 47 ÷ 55%.

The objective of the invention is to develop a method for producing a catalyst for the polymerization of butadiene and copolymerization of butadiene with isoprene, which has high activity.

The problem is achieved in that in the claimed method for producing a catalyst for the polymerization of butadiene and copolymerization of butadiene with isoprene by the interaction of components, including the connection of a rare-earth element, conjugated diene to trialkylaluminum (Alk ₃ Al), exposure of the reaction mixture and the subsequent introduction of diisobutylaluminium amide reddenyl amide and alkylidene element and conjugated diene, which is used piperylene, served in trialkylaluminum and the process is carried out at a molar the ratio of trialkylaluminum: compound of the rare-earth element: piperylene: diisobutylaluminum hydride: alkylaluminium halide is 6 ÷ 12: 1: 1 ÷ 20: 6 ÷ 12: 1,8 ÷ 3, respectively. The essence of the process is that first, a rare-earth compound and piperylene are introduced into a hydrocarbon solution of trialkylaluminum with stirring in an inert gas atmosphere and ambient temperature and the reaction mass is maintained for at least 10 minutes at 20 ÷ 60 ° С, after which DIBAG and alkylaluminium halide are added . It should be noted that until the introduction of the last two ingredients, the reaction mixture can be stored without changing properties for a long time (> 20 days). As a rare-earth element compound, carboxylates formed by an individual lanthanide - neodymium (TU 48-4-186-72) or a technical mixture of rare-earth metals, the so-called "Didim", containing at least 85% neodymium and praseodymium from the sum of all incoming metals (TU) are used HELL 11.46-89), and organic acids, for example naphthenic, α and α 'branched monocarboxylic acids.

As trialkylaluminum, triisobutylaluminum or triethylaluminum (Et ₃ Al) are used.

As the aluminum alkyl halide, ethyl aluminum sesquichloride (EACC), diisobutyl aluminum chloride (DIBAC), isobutyl aluminum dichloride (IBADC), and isobutyl aluminum sesquichloride (IBNX) are used.

The components of the catalyst, with the exception of piperylene, are introduced as a solution in a hydrocarbon solvent. Aliphatic (e.g., gasoline, hexane), aromatic (e.g., toluene), cycloaliphatic (e.g., cyclohexane) hydrocarbons may be used as a solvent.

The catalyst matures from 0.5 hours at 40 ° C to 10-15 hours at 20 ° C, after which it is used for (co) polymerization of butadiene.

The polymerization of butadiene and the copolymerization of butadiene with isoprene is carried out at a temperature of 0 ÷ 120 ° C, preferably 30 ÷ 70 ° C, in an organic solvent, for example gasoline, hexane, cyclohexane, toluene or mixtures thereof.

The following are examples illustrating the invention.

Example 1

In a glass reactor with a magnetic stirrer, previously evacuated, heated and filled with dry argon, 2 ml of a TIBA solution in toluene with a concentration of 1 m / l are loaded, stirring is turned on and 1 ml of a solution of neodymium neodecanoate in toluene is introduced at room temperature (concentration 0.22 m / l) and 0.022 ml piperylene. The reaction mixture was kept for 10 'at 60 ° C, then cooled to room temperature and 1.4 ml of DIBAG toluene solution with a concentration of 1.1 m / l and 0.5 ml of DIBAC solution (concentration of 0.88 m / l were added with stirring) ) The molar ratio of TIBA: REE: piperylene: DIBAG: DIBAC is 9: 1: 1: 7: 2. The resulting mixture was stirred for 0.5 hours at 40 ° C, after which it was used as a catalyst.

In a glass ampoule with a capacity of 80 ml, previously evacuated, heated and filled with dry argon, 40 ml of a solution of butadiene in gasoline containing 3.25 g of butadiene are loaded. The ampoule is thermostated at 50 ° C and 0.134 ml of the catalyst solution is added via syringe. After 30 minutes, the polymerization is interrupted.

The polymer yield is 2.99 g (92 wt.%).

The content of 1.4 cis units is 98.1%.

Intrinsic viscosity: 3.2 dl / g.

The polydispersity coefficient is 3.0.

Example 2

In a glass stirred reactor pre-evacuated, heated and filled with dry argon, 2 ml of a solution of TIBA in hexane (concentration 1 m / l) are charged, with stirring and at room temperature 1.5 ml of 0.22 neodymium-hexanoate in hexane with a concentration of 0.22 are introduced m / l and 0.165 ml piperylene. The reaction mixture was incubated for 2 hours at 20 ° C, and then 3.6 ml of DIBAG in hexane (concentration 1.1 m / l) and 1 ml of an EACC solution (conc. Cl, 0.99 m / l) were added sequentially with stirring. The molar ratio of TIBA: REE: piperylene: DIBAG: EASC (Cl) is 6: 1: 5: 12: 3. The resulting mixture was incubated for 15 hours at 20 ° C, and then used as a catalyst.

In a glass ampoule with a capacity of 80 ml, previously evacuated, heated and filled with argon, 40 ml of a solution of butadiene in hexane containing 3.25 g of monomer are loaded.

The ampoule is thermostated at 30 ° C and 0.148 ml of catalyst is added via syringe. After 30 minutes, the polymer was isolated.

The output of polybutadiene is 3.19 g (98 wt.%).

The content of cis-1,4-units is 97.5%.

Intrinsic viscosity 3.0 dl / g.

The polydispersity coefficient is 3.2.

Example 3

A glass stirred reactor pre-evacuated, warmed up and filled with dry argon is charged with 4 ml of a TIBA solution in gasoline (concentration 1 m / l) and 1.5 ml of neodymium neodyanoate in gasoline is introduced at room temperature with stirring (concentration 0.22 m / l ) and 0.66 ml of piperylene. The reaction mixture was incubated for 30 minutes at 40 ° C and then 1.8 ml of DIBAG with a concentration of gasoline of 1.1 m / l and 0.66 ml of IBASX (conc. Cl 10.9 m / l) were added sequentially with stirring.

The molar ratio of TIBA: REE: piperylene: DIBAG: IBASH (Cl) is 12: 1: 20: 6: 1.8.

The mixture was incubated for 10 hours at 20 ° C and used as a catalyst.

In a glass ampoule prepared as in Example 2, 40 ml of a solution containing 3.25 g of butadiene in cyclohexane was charged.

The ampoule is thermostated at 70 ° C and 0.157 ml of catalyst is added via syringe.

After 30 minutes, the polymer was isolated.

The yield of polybutadiene is 3.09 g (95%).

The intrinsic viscosity is 3.4 dl / g.

The polydispersity coefficient is 2.9.

Example 4

2.5 ml of Et ₃ Al with a concentration in toluene of 0.8 m / L are loaded into a stirred reactor prepared in analogy to Example 3, and 1 ml of neodyanoate with a concentration of 0.22 m / L in hexane and 0 are introduced with stirring at room temperature. 11 ml piperylene. The reaction mixture is stored until use at room temperature for one day, and then 1.8 ml of a solution of DIBAG in toluene with a concentration of 1.1 m / l and 0.5 ml of a solution of IBADC in toluene are added successively with stirring (Cl concentration is 0, 88 m / l). The molar ratio of Et ₃ Al: REE: piperylene: DIBAG: IBADC (in Cl) is 9: 1: 5: 9: 2. The mixture was incubated for 10 hours at 20 ° C and used as a catalyst.

In a glass ampoule prepared as in Example 2, 40 ml of a solution containing 2.76 g (51.1 mmol) of butadiene and 0.49 g (7.2 mmol) of isoprene in cyclohexane are loaded. The mass ratio of butadiene and isoprene is 85:15. The ampoule is thermostated at 60 ° C and 0.157 ml of catalyst is added.

The copolymer yield in 90 minutes is 90%.

The copolymer contains 98.2% of cis-1,4 units.

The intrinsic viscosity is 3.2 dl / g.

The polydispersity coefficient is 3.4.

Example 5

2 ml of TIBA in toluene (1 m / L concentration) are loaded into a stirred reactor, analogous to Example 3, and 3.0 ml of Didim 2-ethylhexanoate in hexane with a concentration of 0.11 m / L and 0.33 ml piperylene are added with stirring. The reaction mixture was incubated for 20 days at room temperature and then successively introduced with stirring 3.6 ml of a solution of DIBAG in toluene with a concentration of 1.1 m / l and 0.83 ml of a solution of EAC (Cl concentration 0.99 m / l). The molar ratio of TIBA: REE: piperylene: DIBAG: EASC (Cl) is 6: 1: 10: 12: 2.5.

The resulting mixture was incubated for 0.5 hours at 40 ° C and used for copolymerization of butadiene with isoprene.

In a glass ampoule prepared as in Example 2, 40 ml of a toluene solution of a mixture of monomers containing 2.44 g (45.2 mmol) of butadiene and 0.81 g (11.9 mmol) of isoprene are loaded, the mass ratio of monomers is 75:25 . The ampoule is thermostated at 60 ° C and 0.169 ml of catalyst is added.

After 30 minutes, the copolymer is discharged.

The product yield is 90%.

The copolymer contains 98.0% cis-1,4 units.

Intrinsic viscosity 2.9 dl / g.

The polydispersity coefficient is 3.4.

Thus, the proposed method allows to obtain a catalyst for the polymerization of butadiene and its copolymerization with isoprene, which has increased activity.

Claims (1)

A method of obtaining a catalyst for the polymerization of butadiene and the copolymerization of butadiene with isoprene by the interaction of components comprising a rare-earth element compound, a conjugated diene and trialkylaluminium, exposure of the reaction mixture and the subsequent introduction of diisobutylaluminum hydride and alkylaluminum halide, characterized in that the rare-earth compound of which is used served in trialkylaluminum and the process is carried out at a molar ratio of trialkylaluminum: compound rare earth element: piperylene: diisobutylaluminium hydride: alkylaluminium halide (according to Cl) equal to 6 ÷ 12: 1: 1 ÷ 20: 6 ÷ 12: 1,8 ÷ 3.