CS269311B1 - A method for increasing the activity of a heterogenized catalyst for addition reactions - Google Patents

Abstract

a method of increasing the activity of a heterogeneous catalyst for addition reactions based on copper amino complexes bound to polymeric organic supports, consisting in that a complex catalyst of the CuCl type on an amino-substituted macroporous copolymer of styrene, 2-hydroxyethyl methacrylate, or 2,3-epoxypropyl methacrylate, crosslinked with divinylbenzene or ethylene dimethacrylate, where said copolymer contains 1 to 11 mmol/g of amino groups, is treated with amines of the general formula RR^NH where R ■ alkyl of 3 to 6 carbons and R*- H or R, in a ratio to the weight of the catalyst in a ratio of 0.1 to 1, wherein the activation of the heterogeneous catalyst takes place in acetonitrile as a solvent.

Description

The invention relates to a process for increasing the activity of a heterogeneous catalyst for addition reactions based on copper amino complexes bound on an organic polymeric support by pre-reaction treatment of the catalyst with amines in a suitable solvent which increases the activity of the original catalyst in:

R-CH »CHR '+ CCl ₄ R-CHCl-CHR'-CCl-j,

Wherein R is alkyl with a chain or aryl, R '= H or R.

Addition reaction products (of which mainly 1,1,1,3-tetrachloro-3-phenylpropane is an important intermediate in the production of cinnamic acid) are useful as intermediates in the production of chemical products for the pharmaceutical, agrochemical and food industries.

The current preparation of type II polyhalohydrocarbons is based on the homogeneously catalyzed addition of carbon tetrachloride to alkenes, where a copper complex with primary, secondary or tertiary amines is used as a catalyst (Czech author's certificate 3. 209 347, 1982), or the complex is formed in situ from compounds copper and primary or secondary amines (Czech author's certificates no. 241 686, 1984} Hájek M., Šilhavý P., Málek J .: New synthesis of cinnamon aldehyde: Chem. Industry 35, 423 (1985)). The disadvantage of homogeneously catalyzed addition is the difficulty of removing catalysts from the reaction mixture.

This shortcoming is overcome by the use of immobilized catalysts, polymer complexes bound to the polymer to the organic support via polymer-bound amino groups. A macroporous copolymer of styrene and divinylbenzene or esters of methacrylic or acrylic acid and containing 1 to 40% of crosslinking agent has been described in the form of a polymeric carrier. However, the addition catalyzed by these immobilized catalysts is still disadvantaged by lower yields compared to homogeneously catalyzed additions. This disadvantage of using immobilized catalysts is partially eliminated by increasing the activity of the immobilized catalyst by doping with amines in a suitable solvent.

The invention therefore relates to a process for increasing the activity of a heterogeneous catalyst for addition reactions based on copper amino complexes bound to polymeric organic supports, where a CuCl-type complex catalyst on an amino-substituted macroporous copolymer of styrene, 2-hydroxyethyl methacrylate and 2,3-epoxypropyl methacrylate, crosslinked with divinylbenzene or ethylene dimethacrylate, wherein said copolymer contains 1 to 11 millimoles / g of amino groups, amines of the general formula RR NH, wherein R alkyl of 3 to 6 carbons and R * ^- - H or R, in a ratio of to a catalyst weight in the range of 0.1 to 1, the activation of the heterogenized catalyst taking place in acetonitrile as solvent.

CS 269 311 Bl

The pretreatment treatment of the immobilized catalyst ae takes place at normal temperature with stirring with a vibrating stirrer for 2 to 5 hours. During this time, there is a partial back-elution of the copper complex from the polymer bonds and a redistribution of the ligands in the catalytic complex, which leads to a longer activity in the addition reaction. The resulting increase in the activity of the immobilized catalyst depends on the type of polymeric support, the degree of its loading with the copper complex and the relative amount of amine added relative to the amount of copper bound in the original complex and the type of amine dopant.

The following examples characterize the invention without limiting its scope in any way.

Example 1

1.02 parts by weight of a copolymer of polystyrene and divinylbenzene containing 2.3 2 mmol of amino groups per gram of polymer with a specific surface area of 6.3 m 2 / g, a density of 640 g / l and a grain size of 0.3 to 0.55 mm reacted and 0.1 49 parts of CuCl dissolved in 14 parts of acetonitrile under an inert atmosphere. After stirring with a vibratory stirrer for 4 hours, washing 5 times with 1 part acetonitrile, suction filtration and vacuum drying, an immobilized catalyst containing 1.65 mg eq. Cu / g.

0.170 parts by weight of such a catalyst was used to add 6.7 parts by weight of tetrachloroethane to 0.38 parts by weight of styrene. The addition took place at 70 ° C in a tempered, stirred batch reactor under an inert atmosphere. After 6 hours of reaction, the amount of 1,1,1,3-tetrachloro-3-phenylpropane in the reaction mixture was 16.3% yield by gas chromatography analysis.

To 0.29 part by weight of the immobilized catalyst prepared above together with 1.6 part of acetonitrile was added 0.07 part by weight of n-butylamine, and the mixture was equilibrated at normal temperature with occasional stirring under an inert nitrogen atmosphere for 4 hours. After filtration and washing 4 times with 1 part acetonitrile and vacuum drying, an amine-doped immobilized catalyst containing 1.52 mg eq. Cu / g.

0.22 parts by weight of this catalyst was used to add 8 parts of carbon tetrachloride to 0.453 parts of styrene at 70 ° C under exactly the same conditions. After 6 hours, 22.3% of styrene reacted with 1,1,1-tetrachloro-3-phenylpropane. Doping the immobilized catalyst with a low molecular weight amine increases the addition yield by 1.4-fold.

Example 2

Bound catalyst with a content of 2.89 mgeq. Cu / g was in this case prepared on copolymers of polystyrene with divinylbenzene with a grain size of 0.3 to 0.5 mm and a density of 650 g / l, which contained 2.5 mmol of amino groups / g. 1.01 parts of copolymers were reacted with 1.21 parts of CuCl in 16 parts of acetonitrile. The polymer saturation and finishing were similar to Example 1.

0.34 part of this immobilized catalyst was doped with 0.108 part of n-butyl CS 269 311 B1 3 lamin in 1.6 part of acetonitrile. Following the same procedure as in Example 1, a doped immobilized catalyst containing 1.83 mg eq. Cu / g.

Both catalysts were used to add carbon tetrachloride to styrene under the same conditions and at the same reactant ratio as in Example 1. In the case of the undoped immobilized catalyst, 4.0% yield was obtained after 8 hours, in the case of the primary amine modified catalyst 7.1% yield 1 1,1,1-tetrachloro-3-phenylpropane. Treatment of the anchored catalyst prior to addition of the reaction with the primary amine resulted in a 1.8-fold increase in yield after Bhod. reaction.

Example 3

5.46 parts by weight of copolymers of 2,3-epoxypropyl methacrylate with 40% by weight of diethylenetriamine-modified ethylene dimethacrylate with a primary amino group content of 3.73 mmol / g and a specific surface area of 68 m 2 / g and a grain size of 20 to 120 .mu.m were reacted with 2.48 parts of CuCl. dissolved in 70 parts of acetonitrile and treated according to Example 1 to give an immobilized catalyst containing 1.61 mg eq. Cu / g.

0.3 part by weight of this catalyst was used for addition to styrene, which after 10 hours of reaction gave 1.8% of theory of 1,1,1-tetrachloro-3-phenylpropane.

0.151 part of the above-prepared immobilized catalyst was reacted with 0.0267 parts of n-butylamine to prepare a doped immobilized catalyst containing 1.13 mgeq. Cu / g, 0.115 part of which was used for the addition reaction, which produced 6.1% of the additive after 10 hours of reaction. Doping of the immobilized catalyst with a low molecular weight amine increased the yield 3.4-fold in this case.

Example 4

From the 3.5 copolymer support based on polystyrene-divinylbenzene used in Example 2, this time an immobilized catalyst containing 2.02 mgeq was prepared by saturating with 1.04 parts of CuCl in 7.8 parts of acetonitrile. Cu / g.

0.236 part of this catalyst was reacted with 0.154 part of dibutylamine in 1.6 parts of acetonitrile. Following the same procedure as in Example 1, a doped immobilized catalyst containing 1.80 mg eq. Cu / g.

By comparing the addition reactions of carbon tetrachloride to styrene, performed under experimental conditions. 1, using the immobilized catalyst without treatment and the pre-treated catalyst, it was found that after 10 hours of reaction, 1,1,1-tetrachloro-3-phenylpropane was obtained in a yield of 17.7% compared to 14.7% for the catalyst. unmodified.

Example 5

The immobilized catalyst prepared in Example 4 was pretreated with 0.28 part of a catalyst containing 2.02 mgeq. Cu / g was left

CS 269 311 Bií '.' .

react and C, 2O8 parts of n-butylamine in 1.6 parts of acetonitrile. After the treatment described in Example 1, an immobilized catalyst containing 1.45 mg eq. Cu / g.

By comparing the addition yield catalyzed by it with the addition yield catalyzed by the pre-reaction amine untreated catalyst, the yield ratio of 1,1,1,3-tetrachloro-3-phenylpropane after 10 hours of reaction was found to be 27 »2% versus 14.7% (1.85-fold increase). .

Example 6

The immobilized catalyst obtained according to Example 4 with a content of 2.02 mgeq. Cu / g was pretreated by reacting 0.248 part of this catalyst with 0.109 part of n-pentylamine in 1.6 parts of acetonitrile under vibratory stirring. The immobilized catalyst obtained contained, after washing, 1.45 mg eq. Cu / g.

By comparing the addition yields catalyzed by the original and treated catalyst, it was found that the treated catalyst gave a 15.9% yield after 8 hours of reaction versus a 9.4% yield of 1,1,1-tetrachloro-3-phenylpropane on the untreated catalyst (1.7-fold increase).

Example 7

The same catalyst, this time doped with 0.093 parts of secpropylamine (0.261 parts of catalyst), after treatment as described in Example 1, gave, after 8 hours of addition, a 17.5% yield of 1,1,1,3-tetrachloro-3-phenylpropane versus 9. 4 & the yield obtained on the original catalyst (1.9-fold increase).

Example 8.

0.256 part of the immobilized catalyst prepared in Example 4 was doped with 0.094 part of sec-butylamine according to the procedure described in Example 1. With 0.192 part of the thus prepared immobilized catalyst, which contained 1.42 mg eq. Cu / g was added carbon tetrachloride to styrene, which yielded 13.6% of 1,1,1-tetrachloro-3-phenylpropane after 8 hours, in contrast to the addition of the original catalyst, which gave a yield of 9.4%. (1.45-fold activation).

Claims (2)

OBJECT OF THE INVENTION Process for increasing the activity of a heterogeneous catalyst for addition reactions based on copper amino complexes bound to polymeric organic supports, characterized in that the CuCl-type complex catalyst on amino-substituted macroporous copolymers of styrene, 2-hydroxyethyl methacrylate and 2,3-epoxypropyl methacrylate, crosslinked with divinylbenzene or ethylene dimethacrylate, where the copolymer contains 1 to 11 millimoles / g of amino groups, are treated with amines of the general formula P.P. NH, where R = alkyl of 3 to 6 carbons and R = H or R, relative to the weight of the catalyst in the range of 0.1 to 1, the activation of the heterogenized catalyst taking place in acetonitrile as solvent.