SU1361134A1 - Method of producing neopentylglycol - Google Patents

Abstract

The invention relates to polyhydric alcohols, in particular, neopentyl glycol (NPG), which is used in the manufacture of synthetic lubricating oils and plasticizers. The purpose of the invention is to reduce the technology of reducing the loss of isomaldehyde (SIMA) and increasing the selectivity of the process. The training of NPGs is carried out by condensation of an IMA with technical formalin in the presence of triethylamine in an aqueous medium, first at 20 ... 25 C for 30-35 minutes, then the temperature is raised and the process is carried out at 70 ... Isobutanol with a mass ratio of 2,5 ... 3: 1 oxypivaline aldehyde, and unreacted IMA, triztilamine (which are returned in the process) and water are distilled off. The residue containing oxypivaline aldehyde is subjected to hydrogenation. The desired product is recovered by rectification. The method allows to simplify the process by eliminating alkali from the condensation stage, using technical formalin, and reducing the loss of IMA. Selectivity at the stage of condensation 98.8 ... 99.2% с s (L 05 00 4

Description

The invention relates to the main organic synthesis, to the production, of polyhydric alcohols, in particular neopentyl glycol, which is used in the manufacture of synthetic lubricating oils, plasticizers and other products of organic synthesis.

The purpose of the invention is to simplify the technology, reduce the loss of isobutyraldehyde and increase the selectivity of the process.

The goal is achieved by the condensation of isobutyric aldehyde with formaldehyde in an aqueous solution, technical formalin is used, the condensation is carried out in triethylamine, first for 30 ... 35 minutes, then raised

ten

the presence of 20 ... 25 C,

temperature and continue the reaction at 70 ... 75 C, isobutanol is added to the obtained condensation with a mass ratio of 2.5 ... 3: 1 oxypivalaldehyde and rectification of unreacted isobutyraldehyde, triztilamine, which are returned to the process, and water , followed by hydrogenation of crawled condensation products containing oxypivalyldehyde. The desired product was rectified.

Example 1. Condensation of aldehydes is carried out at a molar ratio of isobutyraldehyde: formaldehyde 2: 1 in the presence of 0.06 mol of triethylamine per 1 mol of formaldehyde. In the condensation reactor load, g (mol):

Isomaldehyde

Formalin 37%

Triethylamine

13611342

Formaldehyde conversion is 100% with a selectivity of 99.2%.

5 126.8 g of isobutanol (mass ratio of isobutanol: xipivapinaldehyde 2.5: 1) are added to the condensation products, and from the resulting solution of the rectifier at 300 mm Hg. and the temperature of the cube is 100 ... 105 s and 66.19 g of the product of the composition is distilled off, wt%:

Isomaldehyde

Triethylamine

Water

Isobutanol

At the same time, 98% of the amount of isobutyraldehyde, all Triethylamine and 97.5% of water are extracted from condensation products. Get 176,19 g of the cubic residue cocjfaBa, wt.%:

Isomaldehyde

Water 0,36

Isobutanol 70.21

Oxypivaline15

53.24 4.58

37.66 4.52

20

0.41

25

thirty

aldehyde 28,71 Neopentyl glycol isobutyrate 0.05 Neopentyl glycol I hydroxylate 0.25

which is hydrogenated on a nickel chromium catalyst catalyst at 140 s, pressure

35

The mixture is stirred at 20 ... 30 min and then at 70 ... 75 C for 1 h. The end of the reaction is determined chromatographically by the conversion of aldehydes to hydroxypaline aldehyde. Get I. 115,58 g of the reaction mixture composition, may.%:

Isomalty50

aldehyde Oxypivalnaldehyde Isobutyrate non-hydrogen is 50 atm and the feed rate is 1 v / v of catalyst per hour. Isobutanol was distilled off from the hydrogenate and distillation at a pressure of 70 mm pToSTo and a bottom temperature of 165 ° C of 40.55 (0.5) was 51.74 g of neopentyl glycol

(mp. 128 ° C, purity 99.5%). The yield of neopentyl glycol for formaldehyde taken is 99.0% o

72 (1) (O 3.03 (0.03)

31.06 43.77 0., P8

pentylglycol Oxypivalate neopentyl glycol 0.38 Triztilamine. 2.61 Water22.10

55

Example 2 (comparative, carrying out condensation in one step). The condensation is carried out under the conditions of example 1 with the difference that there is no extract at 20 ... 25 C. Obtain 115.58 g of the reaction mixture composition, wt.%: Isomalized

aldehyde31,77

Oxypivalnaldehyde 42,42 Isobutyrate

neopentyl glycol 0.3 Neopentyl glycol hydroxy 0.54

ten

11342

Formaldehyde conversion is 100% with a selectivity of 99.2%.

5 126.8 g of isobutanol (mass ratio of isobutanol: xipivapinaldehyde 2.5: 1) are added to the condensation products, and from the resulting solution of the rectifier at 300 mm Hg. and the temperature of the cube is 100 ... 105 s and 66.19 g of the product of the composition is distilled off, wt%:

Isomaldehyde

Triethylamine

Water

Isobutanol

At the same time, 98% of the amount of isobutyraldehyde, all Triethylamine and 97.5% of water are extracted from condensation products. Get 176,19 g of the cubic residue cocjfaBa, wt.%:

Isomaldehyde

Water 0,36

Isobutanol 70.21

Oxypivaline15

53.24 4.58

37.66 4.52

20

0.41

25

aldehyde 28,71 Neopentyl glycol isobutyrate 0.05 Neopentyl glycol I hydroxylate 0.25

which is hydrogenated on a nickel chromium catalyst catalyst at 140 s, pressure

Example 2 (comparative, carrying out condensation in one step). The condensation is carried out under the conditions of example 1 with the difference that there is no extract at 20 ... 25 C. Obtain 115.58 g of the reaction mixture composition, wt.%: Isomalized

aldehyde31,77

Oxypivalnaldehyde 42,42 Isobutyrate

neopentyl glycol 0.3 Neopentyl glycol hydroxy 0.54

.

Triethylamine 2.61

Water22,1

Formaldehyde 0.26 Conversion of formaldehyde 98.0%, fertility 98.1% o

122.6 g of isobutanol (mass ratio of isobutanol: oxypivaline-aldehyde 2, 5: 1) are added to the condensation products, and 66.89 g of the product of the composition, may,%, be distilled from the solution obtained by distillation under the conditions of example 1

Isomalous

aldehyde53.78

Triethylamine 51 Water37,22

Isobutanol4,48

at the same time, 98% of the amount of isobutyraldehyde, all Triethylamine and 97.5% of water are extracted from condensation products. Receive 171.29 g of the cubic residue of the composition, wt.%:

Isomalous

aldehyde 0.42

Isobutanol69,86

Water0.37

Oxypivalnaldehyde28, 62 Isobutyrate

neopentyl glycol 0.20 Neopentyl glycol oxypivalate 0.36 Formaldehyde 0.17 which is hydrogenated under the conditions of example 1. 51.5 g of neopentyl glyco (tg, 127 ° C, purity 98.5%) were extracted from the hydrogenate under the conditions of example 1 1 The yield of neopentyl glycol for the formaldehyde taken up was 97.6%,

Example 3 (comparative), Condensation is carried out under the conditions of example 1 with the difference that first the temperature is maintained at 20 ,, 25 C for 35 minutes, and then it is raised to 80 ,, 85 C and the reaction is carried out for 1 hour. 115.58 g of the reaction mixture composition, wt.%:

Isomaldehyde aldehyde 30.97. Oxypivalnaldehyde 43,16 Neopentyl glycol isobutyrate 0, 45 Neopentyl glycol oxypivalate. 0.7 Triethylamine 2.61 Water22.1 As a result of condensation at a temperature exceeding 70 ,,,

1344

75 C, formaldehyde conversion reaches 100%, but selectivity decreases to 97.8%, 124.7 g of isobutanol is added to the condensation products (the mass ratio of isobutanol: oxypivaline aldehyde is 2.5: 1), and from the obtained p solution by distillation of Example 1, 66.01 g of product of the composition are distilled off. wt%;

Isoaldehyde aldehyde53, 14 Triethylamine 4.59 Water 37,72 Isobutanol 4.54 and from the condensation products 98% of the contained isoaldehyde, all Triethylamine and 97.5% of water are extracted. Get 174.26 g of the cubic residue of the composition, May,%:

Isomalous aldehyde 0,41 Vodo0,37

Isobutanol69,84

Hydroxypivalnaldehyde 28.62 Neopentyl glycol isobutyrate 0, 3 Neopentyl glycol hydroxy acid 0.46 which is hydrogenated under the conditions of Example 1, 50.95 g of neopentiethgly glycol (t, 1b, 127.5 C, purity 99, 0%). The yield of neopentyl glycol on formaldehyde is 97.0%.

Example 4 (comparative), Condensation is carried out under the conditions of Example 1 with the difference that they first support temperature 20 ... for 30 ,, 35 minutes, and then raise it to 60 ,, 65 ° C and lead the reaction before complete formaldehyde conversion of 2 hours, conversion selectivity 97.6%, Extraction of isobutyric aldehyde, triethylamine and water, hydrogenation of the vat residue and isolation of neopentyl glycol was carried out under conditions of example 1. Extraction of isobutyraldehyde 98.1%, yield of neopentyl glycol was taken formaldehyde 98.9%,

Example 5 Condensation is carried out under the conditions of example 1 with the difference that the molar ratio is isomeric aldehyde: formaldehyde is 1.5: 1. The condensation reactor is charged, g. (mol):

Formalin oil aldehyde 37% - ny TRIethylamine

54 (0.75)

40.55 (0.5) 3.03 (0.03)

Obtain 97.58 g of reaction mixture,

containing, in wt.%: Isomalous

18.51

aldehyde oxypivaline aldehyde isobutyrate neopentyl glycol

Neopentyl glycol oxypivalate

Triethylamine Water

51.66

0.16

0.38

3.1

26.19

Formaldehyde conversion is 100%, the selectivity is 98.8%. The condensation products were diluted with 126 g of isobutanol (mass ratio of isobutanol: oxypiva linaldehyde 2.5: 1), and 48.2 g of product were distilled off from the resulting homogeneous solution under the conditions of example 1, May.%:

36.76 6.30 51.75 3.19

in condensation of collodia, all water.

vat residue

0.21 28.73

0.09

0.21 0.36 70.40 example conditions

1. 51.7 g of neopentylglycol are isolated from the hydrogenation product by distillation (m.p. 127 ,, purity 99%). The yield of neopentyl glycol for formaldehyde taken is 98.5%.

Example 6. The condensation is carried out under the conditions of Example 1, with the difference that the molar ratio is

buty aldehyde: formaldehyde 2.5: 1. In the condensation reactor load, g (mol): Isomalous

aldehyde 90.0 (1.25) Formalin

37% 40.55 (0.5) 3.03 (0.03)

g reactionary mix5

Triethylamine

Get 133,58 mixtures containing

Isomalous

aldehyde

Oxypivalnaldehyde

Isobutyrate

neopentyl glycol

Hydroxyvale

neopentyl glycol

Triethylamine

Water

Formaldehyde conversion is 100%, selectivity is 99.2%. The condensation products were diluted with 127 g of isobutanol (mass ratio Isobutanol oxypivaline aldehyde 2.5: 1), and 83.82 g of product was distilled off from the resulting homogeneous solution under the conditions of example 1.

0

May.%: 40.4 37.87

0.05

0.28 2.27 19.13

0

five

containing, wt.%: Isolated aldehyde Triethylamine Water Isobutanol

With this from

attract 98%

63.1.

3.61

29.71

3.58

condensation products because of the amount of isobutyraldehyde contained, triethylamine, and 97.5% water.

the whole

five

Get 176,76 g VAT residue composition, wt.%:

Oily aldehyde Oxypivalnaldehyde Neopentyl isobutyrate0, 61 28.62

glycol

Hydroxyvale

neopentyl glycol

Water

Isobutanol

0.04

0.21 0 Noda 0.37

70.15

The residue was hydrogenated under the conditions of Example 1. 51.7 g of neopentyl glycol 5 (mp. 128.8 ° C, Purity 99.5%) were distilled from the hydrogenate. The yield of neopentyl glycol for formaldehyde taken is 98.9%.

Example 7 Condensation is carried out under conditions of example 1 with that of 7. It is assumed that 0.03 mol of triethyl amine is taken per 1 mol of formaldehyde. In the condensation reactor load, g (mol

Isomaldehyde 72 (1)

Formalin

37% 40.55 (0.5)

Triethylamine 1.52 (0.015) Obtain 114.07 g of the reaction mixture containing, in wt.%:

Isomalous

aldehyde31,83

Oxypivalnaldehyde44, 16

Isobutyrate

neopentyl glycol 0.09

Hydroxyvale

neopentyl glycol 0, 18

Triethylamine 1.33

Water22,41

100% formaldehyde conversion, 98.8% selectivity, Co-condensation products are diluted with 125.9 g of 1 sobutanol (May the total ratio of isobutanol to oxipine-valinaldehyde is 2.5: 1), and 64.99 g of product is distilled off from the resulting solution under the conditions of example 1 containing wt.%: with

Isomalous

aldehyde 54.73

Triethylamine 2.34

Water 38.31

Isobutanol 4.62 In this case, 98% of the contained amount of isobutyraldehyde, all triztilamine and 97.5% of water are extracted from the products of the condensates.

Get 174.98 g of the bottom residue composition, wt.%:

Isomalous

aldehyde 0.42

Oxypivalnaldehyde 28, 78

Isobutyrate

neopentyl glycol 0.06

Hydroxyvale

neopentylgly-

stake 0.11

Water 0.37.

Isobutanol 70,25 The residue is hydrogenated as in Example 1. 51.79 g of neopentyl glycol, mp, were distilled by distillation. 127 (purity 88%). The yield of neopentyl glycol for the form of Maldehyde 9 is 8.6%.

eight

Yu

15

0

25 0

0

.

five

0

five

five

Example 8. Condensation is carried out under the conditions of example 1 with the difference that 0.1 mol of triztilamine and 1 mol of formaldehyde are taken. In the condensation reactor load, g (mol):

Isomalous

aldehyde72 (1)

Formalin

37% 40.55 (0.5)

Triztilamine 5.05 (0.05)

Get 1 | 7.6 g of a distillation mixture containing, in May.%:

Isomalous

aldehyde 30.57

Oxypivalnaldehyde 43,06

Isobutyrate

neopentyl glycol 0, 07

Hydroxyvale

neopentiplycol ° 0,29

Tretilaminn 4.29

Water 21.73. Conversion to formaldehyde 100%, selectivity 99.1%. The condensation products were diluted with 127 g of isobutanol (mass ratio Isobutanol: oxypivalin aldehyde 2.5: 1), and 68.17 g of product containing by mass% was distilled off from the resulting solution under the conditions as in Example 1:

Isomalous

aldehyde 51.66

Triethylamine 7.41

Water36,53

Isobutanol 4.4, in this case, 98% of the content of the amount of isobutyraldehyde, all triethyl min and 97.5% of water are extracted from the condensation products.

Get 174,98 g VAT residue composition, wt.% 4

Isomalous

aldehyde 0.41

Oxypivalnaldehyde28, 94

Isobutyrate

neopentyl glycol 0, 05

Hydroxyvale

neopentyl glycol 0.09

Water0.37

 Isobutanol 70, 29 The residue is hydrogenated as in Example 1. 51.74 g of neopentyl glycol is distilled from the hydrogenate by distillation (m.p.

913

128, O C, purity 99.5%). Yield of neopentyl glycol for formaldehyde taken 99, .0%.

Example 9 Loading of the feedstock and condensation is carried out under the conditions of Example 1 with the difference that isobut - NOL is added to the condensation product in relation to 3: 1 hydroxy alcohol. To the condensation products, 152.22 g of isobutanol is added, and 66.19 g of the product of the same composition as in Example 1 is distilled from the solution obtained under the conditions of Example 1. 98% of the contained isomaldehyde , all triethylamine and 97.5% water.

Obtain 201.62 g of the cubic residue of the composition, wt.%: Iso-oil aldehyde 0.36 Oxypivalnaldehyde 25,17 Neopentyl glycol isobutyrate 0.04

Neopentyl glycol oxypivalate 0.1

Water0.31

Isobutanol 74,0.1

The residue was hydrogenated as in Example 1. 51, 44 g of neopentyl glycol (mp. 128 ° C, purity 99.5%) were separated from the hydrogenation by distillation. The yield of neopentyl glycol for the formaldehyde taken is 99.2%.

Example 10 (c; equals) The feedstock and condensation were carried out under the conditions of Example 1 with a selectivity of 99.2% with the difference that a isotu-Tanol was added to the condensation product in relation to 4: 1 hydroxyl-dehydrate. 202.96 g of isobutanol are added to the condensation products, and 66.19 g of the product of the same composition as in Example K are distilled under the conditions of Example 1 98% of the contained iso-aldehyde are removed. triethylamine and 97.5% water.

Receive 252.36 g of the cubic residue of the composition, wt.%:

Isoballed aldehyde 0,28 Oxypivalnaldehyde 20,05 Neopentyl glycol isobutyrate 0, 04 Neopentyl glycol oxypivalate 0, 14 Water 0,26 Isobutanol 79,24

 ABOUT

The residue was hydrogenated as in Example 1. 52.0 g of neopentylglycol, 127.6 ° C (99% purity), were distilled from the hydrogenation by distillation. The yield of neopentyl glycol for formaldehyde taken is 99.0%.

Thus, a further increase in the amount of isobutanol at the rectification stage does not lead to an increase in the degree of extraction of isobutyric al-. degida.

Example 11 (comparative). The feedstock and condensation are carried out under the conditions of Example 1 with a selectivity of 99.2% with the difference that isobutanol is added to the condensation product with respect to hydroxyvalyl aldehyde of 1.5: 1. To the condensation products, 76.11 g of isobutanol is added, and 60.38 g of product containing, in wt.%, Is distilled from the solution obtained under the conditions of the example:

Isomalous

aldehyde 53.59 Triethylamine 4.62 Water36.82

Isobutanol 4.97, while 90% of isobutyraldehyde, 92% of triethylamine and 87% of water are extracted from condensation products.

Get 131,31 g VAT residue composition, wt.%:

Isomaldehyde aldehyde 2, 74

Oxypivalnaldehyde 38, 64 Isobutyrate

neopentyl glycol 0,07 Hydroxy neopentyl glycol 0, 15 Triethylamine 0.18 Water. 2.53 Isobutanol 55.68 The residue is hydrogenated as in Example 1, 50.95 g of neopentyl glycol, m.p. 127.5 С (purity 99%). The yield of neopentyl glycol for formaldehyde taken is 97%. Thus, a decrease in the amount of isobutanol does not ensure the completeness of aldehyde, triethylamine and water during rectification.

Example 12 (comparative). The condensation is carried out under the conditions of example 1 with the difference that the mixture is stirred at 20 ... 25 C for 20 minutes. Get 115,58 g of the reaction mixture composition, wt.%:

eleven

Isomalous

aldehyde 31.48

Oxmpivalnaldehyde 43,19

Isobutyrate

neopentyl glycol 0.10

Hydroxyvale

neopentyl glycol 0.38,

Triethylamine 2.61

Water22,1

Formaldehyde 0.13 Conversion of formaldehyde to 99.0% by selectivity of 98.8%.

124.8 g of isobutanol (mass ratio isobutanol: oxypivaline hydroxide 2.5: 1) are added to the condensation products, and 66.58 g of product of the composition% by mass is distilled from the resulting solution by distillation under the conditions of example 1:

Isomalous

aldehyde54,54

Triethylamine 4.55

Water37.40

Isobutanol 51 In this case, 98% of the contained butyric aldehyde, all Triethylamine and 97.5% of water are extracted from the condensation products.

Get 173.80 g of the cubic residue of the composition, wt.%:

Isomalous

aldehyde 0.42

Water0.37

Isobutanol 70.08

Oxypivalnaldehyde 28, 72

Isobutyrate

neopentyl glycol 0, 07

Neopentyl glycol oxypivalate 0.25

Formaldehyde 0.09, which hydrogenates under the conditions of Example 1. Isobutanol is distilled off from the hydrogenated product and 50.84 g of neopentylglycol (m.p. 127.5 s, 99% purity) are isolated by distillation under the conditions of the example. Neopentylglycol yield to take formaldehyde 96.8%.

Example 13 (comparative). Kondenpal is held under the following conditions: Order 6193/27 Circulation: 372

Prog.-Poly. pr-tie, Uzhgorod, st. Project, 4

36113412

measure 1, with the difference that the mixture is stirred at 20 ... for 45 minutes.

The conversion of formaldehyde with a 100% selectivity of 99.2% proves that an increase in the mix-in time does not lead to an increase in selectivity.

The extraction of isobutyric aldehyde, 10-triethylamine and water, hydrogenation of the still residue and the distribution of neopentyl glycol are carried out under the conditions of Example 1.

Extraction of isobutyraldehyde was 98%, the yield of neopentyl glycol was 15 formaldehyde and 99.0%.

The proposed method allows to simplify the process technology using technical formalin, which, in contrast to concentrated formaldehyde by the known method, does not require an additional preparation stage, exclusion of alkali from the condensation process. The method makes it possible to reduce the loss of iso-25 aldehyde and to increase the selectivity at the condensation stage to 98.8-99.2% (versus 96-97%).

Claims (1)

Invention Formula Method for preparing neopentyl glycol condensation of isobutyric aldehyde with formaldehyde in a solvent in the presence of a base with increased temperature with condensate distillation by distillation of unreacted isobutyric aldehyde catalyst and water, followed by hydrogenation of the resulting condensation products containing oxypivaline dehydrate, and separation by distillation of the target product, characterized in that, in order to simplify the technology, to reduce the loss of isomaldehyde, I have an expendant body. formalin, triethylamine is taken as the base, condensation is carried out in water, first at 20 ... 25 C for 30 ... 35 min, then the temperature is raised and the process is carried out at 70 ... 75 С, isobutanol is added to the condensate obtained before rectification in a mass ratio to hydroxybenzene and 2.5 ... 3: 1 Subscription