SU1544762A1 - Method of producing n-isononylphenols - Google Patents

Abstract

The invention relates to higher alkylphenols, in particular, a process for the preparation of N-isononylphenols used as a raw material for the production of water-soluble surfactants, lubricant additives. The goal is to increase the yield and purity of the target product. The process is conducted by alkylation of phenol with a mixture of propylene trimers, 90-92% of which boils at 131-139 ° C and contains 78-80% of olefins with tri- and tetra-substituted double bonds, in the presence of a catalyst — a porous sulfonated copolymer of styrene and divinylbenzene at 70 ° WITH. The desired product is recovered by distillation with selection of the fraction with bp.305-320 ° C. The method allows to increase the yield of para-monoisonylphenols by 4-5%, and their content in the target product - by 9-10% while reducing the impurity of phenol in the target product by 2.4 times. 2 tab.

Description

The invention relates to a process for the preparation of higher alkylphenols, in particular mono-isonylphenols, used as a raw material for the production of water-soluble surfactants, lubricant additives and other chemical products.

The purpose of the invention is to increase the yield and purity of p-isononylphenols.

Example 1. A mixture of phenol and propylene trimers with BP. 128-145 ° С (90.8% boils within the range of 131-139 ° С, the composition of olefins, wt.%: 10; R1R1C CH1 10; РМ1ЦС СНК3 42; R fRaC CRjP (f 38) is heated to 70 С at molar 2: 1 ratio and pass with a flow rate of 6.5 through

catalyst layer - a porous sulfonated copolymer of styrene and 8% divinylbenzene having a total pore volume of 0.29 cm5 / g with an average radius of 380 A, a total static capacity of 4.1 mEq / l and a specific surface area of about 14 m / g loaded into two serially connected reactors. In the first of the reactors, the reaction temperature is maintained at 95 ° C, in the second, 115-120 ° C. At the exit of the second reactor, the alkylate has the following composition, wt%: unprocessed propylene tricyrs 1.4; phenop 31.7; monoisononylphenols 64.1 (orto: para isomer ratio: 8.7: ql, 3); diizonp

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nilphenols 2.8, which corresponds to a yield of monoisononylphenols of 91.5% of the theoretical, including p-mono-isononylphenols of 83.5% (the composition was determined using high performance liquid chromatography).

1000 kg of alkylate of this composition is subjected to distillation and 15.9 kg of unreacted propylene and f trimers, 1 kg of phenol are taken in the I column, 317.7 kg of phenol, 1.9 kg of propylene trimers, 4.0 kg of C4 in the II column. -C-alkylphenols and 14.8 kg of monoizononylphenols (ortho-: para-isomer 88.5: 11.5), in the third column the target product with a boil. 305-320 C at atmospheric pressure: 0.5 kg of phenol, 594.6 kg of monoizononylphenols (ortho: para isomers 6.4: 93.6) and 2.7 kg of diisononylphenols, resulting in a vat mixture of 25 kg n monoizononylphenols and 21.8 kg diisononylphenols. Thus, out of 1000 kg of alkylate, 597.8 kg of the desired product is isolated, containing 0.08% phenol, 99.5% mono-iononylphenols, including 93.6% of the para-isomer (556.5 kg) and about 0.5 % diisononylphenols.

PRI me R 2 (control). Under the conditions of Example 1, a mixture of propylene trimers with bp is used as the alkylating agent. 125-150 C (90% boils within 128-143 C, olefin content, wt.%: R1CH CHR, 15; P, 10; 40; R1R, C CP3R4 35). The composition of the alkylate, wt.%: Unreacted propylene trimers 1,3; phenol 31.7; monoisononylphenols 63.9 (orto: para isomer ratio 15.4: 84.6); diisononylphenols 3.1, which corresponds to a yield of mono-neononylphenols of 91.2% of the theoretical, including p-monoisononylphenols of 77.2%.

1000 kg of alkylate of this composition is subjected to rectification and 16.5 kg of unreacted propylene trimers and 1.2 kg of phenol are taken in the I column, 319.5 kg of phenol, 2.2 kg of propylene trimers in the II column, -. 3.4 kg of C4-C5-alkylphenols and 15.1 kg of monoizononylphenols (ortho: para-isomers 71, 5: 28, “5), in the third column the target product with a boiling point. 300-325 ° C at atmospheric pressure: 1.1 kg of phenol, 586.4 kg of monoizononylphenols (ortho: para-isomers of 13.6: 86.4) and 2.8 kg of diisononylpheno, giving a mixture of 27.5 in the vat residue kg p-monoizononilphenolov and 24.3 kg diisononylphenol. Thus, out of 1000 kg of alkylate, 590.3 kg of the desired product is isolated, containing 0.19% phenol, 99.3% monoisononylphenols, including 86.4% of the para-isomer (506.9 kg) and about 0.5 % diisononylphenols.

The data on the use of other fractions as alkshruyushchy agent are presented in Table. 1 and 2.

Example 3. A mixture of phenol and propylene trimers with so Kip. 127-145 ° G, (90% boils in the range 131-139 ° C, olefin content, wt.%: 8.5; 12; R, P С, SNRE D1; P RjOCP R, 38.5) molar 3: 1 ratio is reacted as in Example 1 and an alkylate of the following composition is obtained, wt%: unreacted propylene trimers 0.8; Phenol 46,9; monoisononylphenols 51.0 (orto: para isomer ratio: 6.5: 93.5); diiononylphenols 1,3, which corresponds to the yield of monoizononylphenols 94.5% of theoretical, including p-monoizonilphenolov 88.4%.

When rectifying from 1000 kg of alkylate, 486.6 kg of the desired product is isolated, containing 0.08% phenol, 99.4% monoitononylphenols, including 95.0% of the para-isomer (462.2 kg), and about 0.5 % diisononylphenols.

PRI me R 4. A mixture of phenol and propylene trimers with so Kip. 129-145 ° С (92% boils within 131-139 ° С, olelin content, wt.%: 10;, 12; R OCHRj 43; R, R, R 35) in a molar ratio of 2.5: 1 exposes the interaction as in example 1 and get alkylate of the following composition, wt.%: unreacted trimers of propylene 1,1; phenol 40.3; monoichononylphenols 56.7 (orto: para isomer ratio 10.5: 89.5); diisononylphenols 1.9, which corresponds to a yield of monoisononylphenols of 93.0% of the theoretical, including p-monoizononylphenols of 83.2%.

For rectification, 530.4 kg of the target product containing 0.11% phenol, 99.4% monoisononylphenols, including 92.1% of the para-isomer (487.0 kg) and about 0, are isolated from 1000 kg of alkylate. 5% dinzononylphenolone.

When broadening the boiling range of the initial mixture of propylene trimers, the content of tri- and tetrasubstituted olefins in them decreases and the yield of p-mono-isonylphenols decreases, the conditions for distillation separation of alkylation products deteriorate, as can be seen from Example 2 (control).

Further narrowing of the boiling range of the mixture of propylene tricyrs is impractical, since the content of tri- and tetra-substituted olefins does not rise above 80%, and the resources of the initial olefin feed are reduced.

Lowering the boiling point of the fraction of the target product to less than 305 С increases the content of o-mono-isononylphenols and phenol in it. An increase in the boiling point of more than 320 ° C leads to an increase in the content of diisononylphenols in the target product, which deteriorates its quality.

Thus, the proposed method allows an increase in the yield of p-monoisononylphenols on average by 4–5%, and their

content in the target product on

9-10%, which significantly improves its quality, while significantly lowering the impurity content of phenol in the target product (7.4 times).

Claims (1)

Invention Formula The method of obtaining p-isononylphenols by alklycating phenol with unsaturated compounds at elevated temperature in the presence of a porous sulfonated copolymer of styrene and divinylbenzene as a catalyst, followed by separation of the target product by rectification of the reaction mixture, in order to increase the yield and purity of the target product, as an unsaturated compound, use propylene trimer mixture, 90-92% of which boils in the range of 131-139 ° С and contains 78-807 olefinic compounds with tri- and tetra-substituted d oynymi bonds, while rectification selected fraction boiling at 305-320 ° C. table 2