JPH03181448A - Preparation of polyoxyalkyleneglycolamine - Google Patents

Abstract

PURPOSE: To obtain polyoxyalkylene glycolamine easily, by reacting a specified compound as a feedstock with ethylene oxide, propylene oxide, etc., subjecting the product to amination and cleaving the tertiary butyl group with a halogenic acid.

CONSTITUTION: A compound of formula I (R₁ is the same or different H, -CH₃ or -C₂H₅) as a feedstock is reacted with ethylene oxide, propylene oxide, 1,2- butylene oxide or its mixture. The reaction product is subjected to amination, followed by cleavage of the tertiary butyl group with a hydrohalic acid to obtain a compound of formula II (R is H, -CH₃, -C₂H₅; x is 0 to 50). An excess amount of hydrochloric acid or hydrobromic acid is used as the halogenic acid.

COPYRIGHT: (C)1991,JPO

Description

[Detailed description of the invention] The present invention relates to a method for producing aminoalcohols.

Amino alcohols are a desirable and well known class of compounds. U.S. Patent No. 3,231.619 is
Similar to U.S. Pat. No. 4,612,335, it describes a method for producing amino alcohols.

It would be desirable to provide a simple method for producing amino alcohols containing primary amino and hydroxyl groups on each molecule.

Method for producing a polyoxyalkylene compound having a structure: R, R (x=O~50, R=H, CHs, C2■6) and having a molecular weight of 200 to 4,000 and having a primary amino group and a primary hydroxyl group reacts a compound of the formula: % formula % (wherein R is Hl-CHs or -CHaCH-) with ethylene oxide, propylene oxide, and/or 1,2-butylene oxide or mixtures thereof, aminating the product of the reaction;
The process consists of cleaving the tertiary butyl group of the aminated compound using an acidic reagent.

The method of the present invention is characterized in that each molecule has a primary amino group at one end and a primary hydroxyl group at the other end, and has a molecular weight of 200 to 4.00.
0 polyoxyalkylene polymer. This can be achieved by utilizing three known reactions, with careful selection of starting materials and reactants. The reaction formula is shown below: CH.

H R,R (R=H%CH,,C,H.

R1=H, CHs, CJ-x=O~50) Reaction I shows the alkoxylation of blocked ethylene, propylene or butylene glycol. In order to obtain primary hydroxyl groups on the final amino alcohol, tertiary butyl ether is preferred; the epoxide can be ethylene oxide, propylene oxide or butylene oxide. Alkoxylation reactions are known in the art and are catalyzed by potassium or sodium hydroxide. For example, US patent cylinder 3.
No. 535,307 describes common alkoxylation techniques that are useful in the present invention and are incorporated herein by reference. Other known methods of alkoxylation may also be utilized in the present invention.
The type of epoxide used also affects the determination of the solubility of the final material. For example, ethylene oxide adducts are usually replaced by propylene oxide adducts. and butylene oxide adducts.The desired molecular weight will be determined by the amount of epoxide added to meet the end user's objectives.Thus, one skilled in the art will would be able to control both the water solubility and the molecular weight of the substances of Reaction I.

Reaction ▪ shows the amination of the alkoxylated material from reaction I. This amination of polyoxyalkylene alcohols is described, for example, in US Pat. No. 3,654,370.

The aminated alcohol obtained from one reaction is then reacted with a strong acid such as hydrochloric acid. A sufficient amount of acid is required to neutralize the amine, and a significant excess of acid is required to provide the acidic conditions necessary for cleavage of the tertiary butyl group. Those skilled in the art will be able to determine appropriate conditions for cleavage, including temperatures from room temperature to 150°C and pressures low enough to drive the cleaved isobutylene from the reaction mixture. For example, atmospheric pressure can be used, but any pressure can be used if the described results are obtained. the result,
The tertiary butyl end of the molecule is cleaved and replaced by a primary hydroxyl group.

Thus, this reaction scheme results in the production of a polyoxyalkylene amino alcohol of variable molecular weight containing a primary hydroxyl group on one end and a primary amino group on the other end. Acids useful in cleavage reaction (1) have been found to be substances such as hydrochloric acid or hydrobromic acid. Other substances such as sulfuric acid, AmberlystO15 (acidic ion exchange resin), Zeolite@ZM-8 (sodium aluminum phosphate) and polyetheramines and Ambe
It was found that salts of rlyst@15 did not work as well.

The following examples illustrate the method of the invention.

This example from the Uratane team uses propylene glycol tertiary butyl ether (Arcosolv PTB, ARCOChem
The preparation of a propylene oxide adduct of icalCo, 1 with a molecular weight of 550 is described.

l of propylene glycol tertiary butyl ether 61b
An O gallon reaction vessel was charged and the reaction vessel was purged with prepurified nitrogen. Furthermore, the reaction vessel was
45.4 g of potassium hydroxide in flake form heated to 5°C
was added and stirred until dissolved. At this point, the moisture content of the raw material was 0.295%. Furthermore, nitrogen stripping was performed until the moisture content was less than 0.1%. Next, propylene oxide (21,31
b) was reacted at 105-115°C and 50 psig. This propylene oxide addition took approximately 4 hours. The reaction mixture was then cooked to equilibrium pressure for 2 hours. The alkaline product was further neutralized at 95° C. by stirring with 270 g of Magnesol 30/40 added as an aqueous slurry. The neutralized product was then stabilized with 6.2 g of di-tertiary-butyl-p-cresol, vacuum stripped and nitrogen stripped, and filtered. The finished product had the following properties: esteric acid value (mg KOH/g) 0.
003 Hydroxyl value (a+g KOH/g)
102 Water (wt%) 0.0
02 pu 8 in isopropanol/water (10:6)
．． 1 color (Pt-Cal 25 Sodium (ppm) 0.5 Potassium (p
pml 0.3 Viscosity (lower, cs) 77 47, 5 100 27, 1x exemplify the

1 filled with nickel oxide/copper oxide/chromium oxide catalyst
, 250 d of polyether (0,8
lb/hrL ammonia C1,201b/hr)% hydrogen hydrogen (48Q/hrl) was supplied.The temperature of the vessel was set to 190
℃ and the pressure was maintained at 2.000 psig. Then, the crude effluent from the container was heated to 70'C and 3.5 mnH.
The sample was stripped for 30 minutes at The product obtained had the following properties: Total amount of amines (+++eg/gl 1.75
Amount of secondary amine (meg/gl) 1.75Total amount of acetylatable substances (meg/g) 200 g of the aminated polyether of Example 2 and 93 g of a 15% aqueous hydrochloric acid solution.
The reaction temperature immediately rose to 58°C, at which point heat was added and the reaction mixture was heated at 92-100°C for 3
．． Heated for 75 hours. The product was then neutralized with 144 g of a 15% aqueous potassium hydroxide solution.

The neutralized product was then vacuum stripped at minimum pressure for 1 hour at 112° C. and filtered using Hyflo 5uppercel. The filtered product was a dark yellow liquid and had the following properties: Total amine content (meg/gl) Total acetylatable substances (meg/gl) corresponding to the CNMR spectroscopy of this product: 2.0 3.3 The following structure +8 mole EO + lO mole P
The O product had the following properties: Acid number (tag KOH/g) 0.
0 Hydroxy acid value (tag KOH/g)
65 Moisture (wt%) 0.13 pH 7,9 color in impropatur/water (10:6) (P
t-Co) 50 Sodium (pp
m) 0.5 potassium (ppm) 1
．． 3 Viscosity (F, cc) 77 108 100 61.3 The polyether alcohol of Example 4 was heated at 210° C. using the nickel/copper/chromium catalyst described in Example 2.
000 psig and liquid hourly velocity 0.75 g/cc-ca
Reductive amination was carried out at t/hr.

Space velocity of polyol is 0.30 g/cc-cat/h
60% of the liquid raw material was ammonia so that r. The properties of the aminated polyether were as follows: Total amount of acetylated substances (+seg/gl) 1.14 Total amount of amines (eg/g) t, 09 Amount of primary amines (meg/gl 1. 09 colors (Pt
-Cot 20YiyiYuYiPi QTianG This example illustrates the production of the corresponding amino alcohol by cleaving the polyether amine of Example 5. Furthermore, it will be shown that this reaction (annihilation of the tertiary butyl group) can be observed using CNMR.

A 2I2 four-neck flask equipped with a stirrer, thermometer, water-cooled condenser, and nitrogen inlet was charged with 500 g of polyetheramine and 139.5 g of 15% aqueous hydrochloric acid solution, and the reaction mixture was heated to 105° C. for 40 minutes. and then maintained at 104-197°C for 3 hours. 100～
Isobutylene was generated violently at 105°C. An additional 6.6 g of 15% aqueous hydrochloric acid solution was added to the reaction mixture, which was heated for an additional hour at 105°C.

Samples were withdrawn at 1 hour intervals for CNMR analysis. At the end of the reaction, the product was neutralized by stirring with 75 g of 45% aqueous potassium hydroxide solution and 34 g of Magnesol 30/40. The neutralized product was vacuum stripped at 125°C and 5m+nHg and passed through a Hyflo 5uppercel filter. , had the following properties: Total amount of acetylatable substances (n+eg/g) 2.25 Total amount of amines (meg/gl) 1.14 Water (wt%) 0.033 The CNMR spectrum of this product shows the structure of According to the CNMR observation, the degree of cleavage was as follows: An example is the third polyether amine from Example 5.
Figure 2 illustrates the bulk preparation of amino alcohols by removing the butyl group.

5.2 lbs of polyetheramine was charged to a 3 gallon reaction vessel that had been previously purged with purified nitrogen.

Then, 689.3 g of a 15% aqueous hydrochloric acid solution was added to the polyetheramine, and the mixture was heated at 105-110° C. for 6 hours. Meanwhile, the exhaust from the reaction vessel was directed to a flare as isobutylene was liberated during the reaction. An additional 31.3 g of 15% hydrochloric acid was added to the reaction vessel and the mixture was
It was heated for an additional 2 hours at 5-110°C. The reaction mixture was then neutralized with 369.9 g of a 45% aqueous potassium hydroxide solution and added as an aqueous slurry.
The mixture was further stirred with 166.4 g of 30/40 for 2 hours. The product was then vacuum stripped at lowest pressure, nitrogen stripped, and filtered using filter acid. The finished product was a dark yellow viscous liquid with the following properties: Total amine content (eg/g1 1.102
Total amount of acetylatable substances (meg/g1 2.232
Water [wt%] 0.18 isopropanol/water (pH 11.5 in 10:61 Sodium (ppm) 5.8 Potassium (p
pn+) 19 Viscosity (T, cs) 77 139 100 72, NM of the product at
The R spectrum showed that 95% of the tertiary butyl groups had been removed.

Claims (6)

[Claims] (1) Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R and R_1 may be the same or different,
H, -CH_2 or C_2H_5, respectively, and x
is 0 to 50), the compound of the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is mixed with ethylene oxide, propylene oxide,
A process characterized in that the product of the reaction is reacted with 1,2-butylene oxide or a mixture thereof, the product of the reaction is aminated, and the tertiary butyl group of the aminated compound is cleaved with a halogen acid. (2) The method according to claim 1, wherein R is H and/or CH_3. (3) The method according to claim 1, wherein R_2 is CH_3. (4) The method according to any one of claims 1 to 4, wherein x is 8. Formula (5): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The compound of ▼ is reacted with propylene oxide, the reaction product is aminated, and the tertiary butyl group of the aminated compound is converted using halogen acid. 2. The method of claim 1, wherein a compound of the formula: ▲ is prepared by cleavage. Formula (6): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The compound is reacted with propylene oxide and ethylene oxide, the reaction product is aminated, and the tertiary butyl group of the aminated compound is converted to a halogen acid. 2. The method according to claim 1, wherein a compound having the formula: ▲ has a mathematical formula, a chemical formula, a table, etc. ▼ is prepared by cleavage using