DD294393A7 - PROCESS FOR PRODUCING MODIFIED POLY (OXYALKYLENE) GLYCOL - Google Patents

Abstract

Process for the preparation of modified poly (oxyalkylene) glycols having molecular weights between 1,500 and 5,000 and having the general formula: R1 (OCH2CH2) x (OCH3CHCH2) yY (CH2CHCH3O) 2 (CH2CH2O) uR2, in which R1 and R2 have the following meaning: {diethylene glycol; dipropylene; Poly (oxyalkylene) glycols; oxyalkylation; Poly (oxyethylene) glycols; Catalyst; Molecular weight (1 500-5 000); Pour point; Temperature}

Description

wherein R is a mono- or polysubstituted, preferably mono- or di-alkyl-substituted alkylene radical having 2-4 carbon atoms in the alkylene chain and having ethyl, methyl, propyl or isopropyl as alkyl substituents, y = 1 to 3, preferably 1 to 2 , in particular 1, and the sum of χ and y is 5 to 30, preferably 10 to 20, wherein neither χ nor ζ is zero, correspond (DE-PS 3420708). The disadvantage of this method is that liquid products can only be prepared up to a molecular weight of 1400.

Object of the invention

The aim of the invention is to extend the known for certain applications range of poly (oxyethylene) glycols to products that can be processed time-saving and energy-saving without liquefaction, have no surface-active properties and can be expected for good biodegradation behavior.

Explanation of the essence of the invention

The invention has for its object to provide a process for the preparation of modified poly (oxyalkylene) glycols with average molecular weights between 1500 and 5000 by addition of alkylene oxides of glycols in the presence of alkaline catalysts to develop the essential properties of poly (oxyethylene) glycols, in particular have their good water solubility, but have a pour point below 22 ⁰ C.

The object is achieved according to the invention by adding to the starting component Y ethylene oxide and propylene oxide in alternating blocks in order and molar ratios corresponding to the general formula

R '(OCH ₂ CH 2) _x - (OCH ₃ CHCH _{2) y} -Y- (CH ₂ CHCH3O) ₁ - (CH 2 CH ₂ O) _u R ^{^} (IV) wherein R ¹ and R ² have the meanings given below:

R "= -KCH ₂ CHCH ₃ O) _n - (CH ₂ CH ₂ OK ₁ I ₁ -H (IVa) R ² = -1 (CH ₂ CHCH ₃ OL ₁ - (CH ₂ CH ₂ O) V ₁ I ₁ -H (IVb)

and Y is a diethylene glycol or dipropylene glycol radical, (y + z) 0 to 3, (x + u) 8 to 14, the sum before Γι and W _{1 is} 2.5 to 15, the sum of S ₁ and Vt 14 to 105 and the number t of repeating structural units is 1 to 6. There are obtained liquid to viscous-liquid poly (oxyalkylene) glycols, the poly (oxypropylene) proportion is only 16 to 19% and therefore have no interfering with the intended applications surface-active properties and for that not from the literature for products with higher poly (oxypropylene) shares known, typical poor biodegradation behavior is expected.

The preparation of the poly (oxyalkylene) glycols takes place by addition of alkylene oxides under reaction conditions known in principle to a, the radical Y in formula (IV) corresponding glycol, while maintaining specific molar ratios between the used Gylkol and the alkylene oxide to be deposited and although from 0 to 3 Mol of propylene oxide and 8 to 14 moles of ethylene oxide per mole of diethylene glycol or dipropylene glycol and, while maintaining specific molar ratios for the sum of the moles of propylene oxide to be added to the sum of the moles of ethylene oxide to be added, namely from 2.5 to 15 to 14 to 105, depending on the number of repetitive structural units.

The preparation of the poly (oxyalkylene) glycols is carried out in detail so that presented in a glass apparatus, the corresponding Gylkol and an alkaline catalyst and in an inert gas atmosphere by means of vacuum at 110 ⁰ C, the water formed is removed. Thereafter, the glycolate is placed in a pressure autoclave or tower reactor, heated to a temperature between 110 to 18O ⁰ C and gaseous alkylene oxide added. Suitable alkaline catalysts are alkali metal hydroxides, alkali metal alkoxides, alkali metal carbonates, but preferably alkali metal hydroxides are used in amounts between 0.1 to 3.0%, preferably 0.1 to 0.3%. The poly (oxyalkylene) glycols according to the invention are liquid to viscous, partially clear products at room temperature and have the required low pour point.

embodiments The process of the invention is explained in more detail in the following examples. example 1

In a glass apparatus, 500 g of dipropylene glycol are introduced, treated with 7 g (0.1 wt .-% based on the final product) of NaOH, purged with nitrogen and heated to remove the resulting water in a water jet vacuum at a temperature of t = 110 ⁰ C. If the glycolate is anhydrous and the desired alkali number has been reached, the alkoxylation begins. For this purpose, 272 g (2.0 mol) of the alcoholate are drawn by vacuum into a pressure autoclave, brought to a temperature of t = 120 to 140 ° C and with stirring 1100g (25mol) of ethylene oxide, 476g (8.2mol) of propylene oxide and 1962g again (44.6 moles) of ethylene oxide in the autoclave. To complete the reaction, the addition of propylene oxide is allowed to continue for a further 2 hours and then the addition of the ethylene oxide is continued for 0.5 hours. Thereafter, the product is removed from the autoclave and analyzed.

Example 2 In a glass apparatus 1100 g of the product prepared according to Example 1 are presented, with 1.2 g (0.1 wt .-%, based on

the final product) NaOH, purged with nitrogen and to remove the water formed in a water-jet vacuum

heated at a temperature of t = 11O ⁰ C. If the glycolate is anhydrous and the desired alkali number has been reached, the alkoxylation begins. For this purpose, 953 g (0.5 mol) of the alcoholates are drawn by vacuum into a pressure autoclave, brought to a temperature of t = 120 to 14O ⁰ C and stirring 105g (1,8τιοΙ) propylene oxide and 506g (11.5mol) of ethylene oxide in the autoclave given. To complete the reaction is allowed to continue for 2 hours after the addition of propylene oxide and after the addition of ethylene oxide for 0.5 hours. Thereafter, the product is removed from the autoclave and analyzed.

Example 3

1.226 g of the product prepared according to Example 2 are treated analogously to Example 2 with 1.2 g of NaOH (0.1 wt .-%, based on the final product), dewatered and 938 g (0.3 mol) of the alkoxide with 58g (1.0 mol ) Propylene oxide and 264g (6.0 mol) reacted ethylene oxide.

Example 4

1009 g of the product prepared according to Example 3 are treated analogously to Example 2 with 1.2 g of NaOH (0.1 wt .-%, based on the final product), dewatered and 840g (0.2 mol) of the alcoholate with 30g (0.5 mol ) Propylene oxide and 169 g (3.8 mol) of ethylene oxide reacted.

Example 5

500g of dipropylene glycol are treated analogously to Example 1 with 6.5 g of KOH (0.1 wt .-%, based on the final product), dewatered and 275g (2.0 mol) of the alkoxide with 1100g (25mol) of ethylene oxide, 336g (5.8mol ) Propylene oxide and reacted again with 1690 g (38.4 mol) of ethylene oxide.

With a tensiometer, the surface tension of a 0.1% aqueous solution was measured and a value of 60 mN / m

determined (the value for a comparable 0.1% aqueous poly (oxyethylene) glycol solution is between 63 to 64 mN / m).

Example β

1000 g of the products prepared according to Example 5 are treated analogously to Example 2 with 1.4 g KOH (0.1 wt .-%, based on the final product), dewatered and 850g (0.5 mol) of the alcoholate with 37g (0.85 mol) Propylene oxide and 288g (6.55mol) reacted ethylene oxide.

Example 7

1100 g of the product prepared according to Example 6 are treated analogously to Example 2 with 1.4 g of NaOH (0.1 wt .-%, based on the final product), dewatered and 950g (0.4 mol) of the alcoholate with CI g (0, 88 mol) of propylene oxide and 202 g (4.6 mol) of ethylene oxide reacted.

Example 8

1100 g of the product prepared according to Example 7 are treated analogously to Example 2 with 1.4 g of NaOH (0.1 wt .-%, based on the final product), dewatered and 903 g (0.3 mol) of the alcoholate with 28g (0.48 mol) Propylene oxide and 153g (3.48 mol) reacted ethylene oxide.

Example 9

1100 g of the product prepared according to Example 8 are mixed analogously to Example 2 with 1.3 g of NaOH (0.1 wt .-%, based on the final product), dewatered and 904g (0.25 mol) of the alcoholate with 35g (0.60 mol) Propylene oxide and 124g (2.8 mol) reacted ethylene oxide.

Example 10

1000 g of the product prepared according to Example 9 are treated analogously to Example 2 with 1.2 g of NaOH (0.1 wt .-%, based on the final product), dewatered and 850g (0.2 mol) of the alkoxide with 16g (0.28 mol) Propylene oxide and 97g (2.2 moles) reacted ethylene oxide.

Example 11 374 g of diethylene glycol are introduced into a glass apparatus, 6 g (0.1% by weight, based on the end product) of NaOH are added,

purged with nitrogen and heated to remove the water formed in a water-jet vacuum at a temperature of t = 110 ° C. If the glycolate is anhydrous and the desired alkali number has been reached, the alkoxylation begins.

For this purpose, 215 (2 mol) g of the alcoholate are drawn by vacuum into a pressure autoclave, to a temperature of

t = 120 to 14O ⁰ C brought and with stirring 232g (4mol) of propylene oxide, 942g (21.4mol) of ethylene oxide, 313g (5.4mol)

Propylene oxide and another 1795 g (40.8 mol) of ethylene oxide added to the autoclave. To complete the reaction is allowed after the addition of propylene oxide for 2 hours and after the addition

of Ethyienoxids for 0.5 hours. Thereafter, the product is removed from the autoclave and analyzed.

Example 12

1000 g of the product prepared according to Example 11 are treated analogously to Example 2 with 1.6 g of NaOH (0.1 wt .-%, based on the final product), dewatered and 876 g (0.5 mol) of the alkoxide with 96g (1.65 mol) Propylene oxide and reacted 429 g (9.75 mol) of ethylene oxide.

Example 13

1250 g of the product prepared according to Example 12 are admixed analogously to Example 2 with 1.7 g of NaOH (0.1% by weight, based on the end product), dewatered and 1104 g (0.4 mol) of the alcoholate with 74 g (1.28 mol). Propylene oxide and reacted 359 g (8.16 mol) of ethylene oxide.

Example 14

11SOg of the product prepared according to Example 13 are mixed analogously to Example 2 with 1.4 g of NaOH (0.1 wt .-%, based on the final product), dewatered and 971 g (0.25 mol) of the alkoxide with 38g (0.65 mol) of propylene oxide and 180 g (4.08 mol) of ethylene oxide.

Example 15 In a tower reactor 670kg (5.0kmol) dipropylene glycol are presented, 15kg of 50% sodium hydroxide solution and added Flushed nitrogen at 110 to 12O ⁰ C anhydrous. To the anhydrous glycolate are added 2 51 okg (57 kmol) of ethylene oxide, 870 kg

(15kmol) propylene oxide and again 3840kg (87.2 kmol) of ethylene oxide attached. To complete the reaction is allowed to react after completion of the Propylenoxidanlagerung for one hour and after the Ethylenoxldanlagerung each half an hour. The reaction product is removed from the reactor after cooling and analyzed.

Mi) a tensiometer, the surface tension of a 0.1% aqueous solution was measured and a value of 61 mN / m

determined (the value for a comparable 0.1% aqueous poly (oxyethylene) glycol solution is between 63 to 64mN / m).

Example 16

1700 g of the product prepared according to Example 14 are analogous to Example 2 with 2.8 g of NaOH (0.1 wt .-%, based on the

Final product), dehydrated and 1563 g (1.0 mol) of the alcoholate with 116 g (2.0 mol) of propylene oxide and 880 g (20.0 mol) Implemented ethylene oxide. According to the formula (IV) given in the following table, the statistical average values for y + ζ, χ + ü, sum

ri + Wt, sum Si + Vi andt according to examples 1 to 16 and in addition the determined pour points, the viscosity at 70 ° C and information on the solubility of the products in water. In comparison, the table contains information on the pour point and the viscosity of the pure poly (oxyethylene) glycols.

table

examples y + z x + u total total t molar mass pour point PEG viscosity PEG Water sp. ri + Wi Sl + V | g / mol ° C +47 mm ² / s (70 ° C) 58 (33% solution) No. POG +50 POG 161 1 0 12.5 4.1 22.3 1 1906 +12 +52 87 303 clearly soluble 2 0 12.5 7.7 45.3 2 3123 + 18 +52 171 482 clearly soluble 3 0 12.5 11.7 65.3 3 4176 +22 +46 292 47 clearly soluble 4 0 12.5 (3.6 86.3 4 5176 + 19 +49 448 90 clearly soluble 5 0 12.5 2.9 19.2 1 1697 +9 +50 73 148 clearly soluble 6 0 12.5 4.6 32.3 2 2372 +15 +51 109 220 clearly soluble 7 0 12.5 6.8 43.8 3 3006 +17 +52 143 314 clearly soluble 8th 0 12.5 8.4 55.4 4 3609 +17 +52 202 412 clearly soluble 9 0 12.5 10.8 66.7 5 4245 +18 +46 266 49 clearly soluble 10 0 12.5 12.2 77.3 6 4811 +17 +50 345 123 clearly soluble 11 2 10.7 2.7 20.4 1 1747 +11 +51 75 258 clearly soluble 12 2 10.7 6.0 39.9 2 2756 +16 +52 143 423 clearly soluble 13 2 10.7 9.2 60.3 3 3880 +16 +45 233 41 clearly soluble 14 2 10.7 11.8 79.4 4 4871 +16 +49 355 105 clearly soluble 15 0 11.4 3.0 17.5 1 1560 +4 52 clearly soluble 16 0 11.4 4.0 37.5 2 2556 +14 110 clearly soluble

POG poly (oxyalkylene) glycol PEG poly (oxyethylene) glycol

Claims (1)

A process for the preparation of modified poly (oxyalkylene) glycols having average molecular weights between 1500 and 5000 by addition of alkylene oxides to glycols in the presence of alkaline catalysts, characterized in that the start component Y ethylene oxide and propylene oxide in alternating blocks in order and molar ratios corresponding to the general formula R ¹ (OCH ₂ CH ₂ ) χ- (OCH ₃ CHCH ₂ ) _Ϋ -Y- (CH ₂ CHCH ₃ O) _^ - (CH ₂ CH ₂ O) _u R 1 where R ¹ and R ² are as defined below: R ¹ = - [(CH ₂ CHCH ₃ O) _n - (CH ₂ CH ₂ O) ₈ JrH
R ² = - [(CH ₂ CHCH ₃ O) w, - (CH ₂ CH ₂ O) _Vl ] _t -H and Y is a diethylene glycol or dipropylene glycol radical, (y + z) is 0 to 3, (x + u) is 8 to 14, the sum of η and Wi is 2.5 to 15, the sum of S ₁ and V ₁ 14 to 105 and the number t of repeating structural units is 1 to 6. Application of the invention The invention relates to a process for the preparation of modified poly (oxyalkylene) glycols with molecular weights of 1500 to 5000, the z. B. as a release agent, lubricants and lubricants, as a binder, as a solvent in cleaning and cleaning agents, as an additive to electroplating baths, for dimensional stabilization and conservation of wood or paper, in cosmetics, in fiber and polyurethane production and as an additive can be used in pesticides. Characteristic of the known technical solutions Poly (oxyalkylene) glycols are addition products of alkylene oxides with di- or polyhydric glycols, which in the conventional use of ethylene or propylene glycol and ethylene and / or propylene oxide of the following general formula HO (CHR ¹ CHJO) ₁ (CH ₂ CHr ¹ OWCH ₂ CHR ¹ O) CH (I) with (a + c) = O, R ¹ = H or = CH ₃ , (a + c) other than O, R ¹ = H, R ² = CH ₃ or R ¹ = CH ₃ , R ² = H. The known liquid poly (oxyalkylene) glycols of this molecular weight range in which the poly (oxyethylene) - and - (oxypropylene) units are arranged in the form of blocks in the molecular chain contain more than 50% of propylene oxide, have surface-active properties and are because of biologically incompletely degradable. Due to their surface-active properties, they are very often used in low-foaming detergent and detergent formulations as dispersants, emulsifiers or the like. used (DE-PS 1467638, US-PS 4017407). This also applies to known poly (oxyalkylene) adducts of the general formula RO (CH ₂ CHR ¹ O) ₁ (CH ₂ CHr ² O) ₀ H (II) with a, b not equal to O, R ¹ = H, R ² = CH ₃ or R ¹ = CH ₃ , R ² = H, R = n-alkyl, which are obtained by addition of alkylene oxides to hydroxyl-containing starting components with n-alkyl radicals to (DE-PS 3207612, US Patent 4263160). On the other hand, poly (oxyethylene) glycols are known for a number of specific properties, such as very good water solubility, volatility, heat resistance, insusceptibility to electrolyte solutions, etc., in many fields, for example as release agents, lubricants and binders, solubilizers for water-insoluble substances, preservatives and humectants , used. The poly (oxyethylene) glycols are mostly used either as a 100% product, as aqueous solutions or in admixture with other poly (oxyethylene) glycols or poly (oxyalkylene) adducts. Pure poly (oxyethylene) glycols with molecular weights between 1500 and 5000 are solid, waxy compounds, which is disadvantageous for many of the applications mentioned, since the products must be liquefied prior to further processing, for example for the preparation of solutions and mixtures, which energy and Costs time and can affect the color of the products. There are also known modified poly (oxyethylene) glycols having molecular weights between 250 to 1400, which have a low freezing point, in the other properties of the conventional poly (oxyethylene) glycols and the general formula HO (CH ₂ CH ₂ O) _x (RO) _y (CH ₂ CH ₂ O), H (III),