SU1118635A1 - Method of obtaining polyaminoalkylphenols - Google Patents

Abstract

THE METHOD OF OBTAINING POPIAMINOALKYLPHENOLS by condensation of phenol with formaldehyde and amines, which is based on the fact that, in order to increase the yield of the target product and improve its quality, phenol with formaldehyde and dialkylamine is first condensed at a mole ratio of 1:

Description

(L

with

00

The invention relates to a process for the preparation of polyaminoalkyl (enols, which are used as epoxy resin holders and compositions based on them. Known methods for the preparation of polyaminoalkylphenols, in particular ethyl diaminomethylphenols (hardener AF-2) and diethylenetriaminomethylphenol, phenylmethylnenol phenols (hardener AF-2) and diethylenetriaminomethylphenol, phenylmethylnenol phenol (hardener AF-2) and diethylenetriaminomethylphenol, phenylmethylnenol phenol (hardener AF-2) and diethylenetriaminomethylphenols, and ethylene diamine monomethylphenols (hardener AF-2) The traditional method of producing such hardeners is the condensation of phenol with formaldehyde and diyl polyamine at a stoichiometric molar ratio of reagents 1, However, these methods determine the comparison However, the yield of the target product is not high and they do not provide hardeners with stable quality indicators. The yield of polyaminoalkylphenols does not exceed 70% of the theoretical one, and the viscosity of these products varies from 500 to 35000 mPa-s. These disadvantages are primarily due to the polydispersity of the reaction According to this method, the occurrence of which in these conditions is accompanied by the formation of significant amounts of volatile and slightly reactive Schiff bases, the appearance of bis- and poly- (oxy-benzyl) -derivatives of polyamines, aminoalkyl phenol-aldehyde oligomers, etc. All these side substances are either distilled off during the synthesis process with water, reducing the yield of the target products and pollutants from the production of hardeners, or remain in the composition of the target products, causing instability of their physicochemical parameters, activity and other valuable properties. In addition, the consumption of formaldehyde and polyamine in side processes leads to the contamination of hardeners with free phenol. For example, in industrial batches, hardeners AF-2 and UP-583 contain up to 30% of free phenol. This increases the hardener’s toxicity and eliminates the possibility of it hardening in materials that are operated indoors, in contact with food products, high-quality gasoline, etc. Therefore, hardeners of the type of polyaminoalkylphenols, obtained by conventional methods, have a limited scope. The closest to the present invention is a process for the preparation of polyaminoalkylphenols, consisting in the condensation of phenol (cresol, apkylphenols, chlorophenol), diaminodicyclohexylmethane or its mixtures with amines such as ethylenediamine, diethylenetriamine, tetramethyldiamine, hexamethylamino, or an amount of iamylah, I am in place for the groups, and I am a way to get a lot of people, and then they will be the same. paraform, acetaldehyde, chloral. In this case, the ratio of components in mol x is taken respectively from 1: 0.3: 0.3 to 1: 3: 3. Preference is given to an equimolar ratio of components, i.e. respectively 1: 1: 1. The product is obtained in a vvde resinous liquid with a viscosity at 1.5-36 Pa-s. Depending on the ratio of the components, the product yield fluctuates 60-85% of theoretical 2. The known composition is characterized by an insufficiently high yield of the target product, as well as a significant content of free phenol in the target product (7-12%) and products of side reactions. The aim of the invention is to increase the yield of the target product and improve its quality. The goal is achieved by the fact that. According to the method for producing polyaminoalkylphenols by condensation of phenol with formaldehyde and imines, phenol is first condensed with formaldehyde and dialkylamine at a molar ratio of 1: (1.10-1.25): 1, respectively, forming the base of mannich in the process - or polyamine. The introduction of an excess amount of formaldehyde relative to phenol and amine in the first stage ensures a sufficiently complete binding of the reagent, as well as securing the future structure of the polyaminoalkylphenol. With the introduction of formaldehyde less than 1.10 mol per 1 mol of phenol, in the intermediate base of manniche, and then in the final hardener, the content of free phenol increases sharply to 8-12%. As a result, the reproducibility of the properties of the target products is worsened and their toxicity increases. With the introduction of more than 1. 25 mol of formaldehyde, the reaction mass tends to delaminate with 3 additions of toluene, which makes the process technologically inconvenient. In addition, the viscosity of both the intermediate Mannich base and the final polyaminoalkylphenol is significantly increased. As amines, you can use aliphatic diamines (ethylenediamine, propylenediamine, hexamethylenediamine, etc.), or other aesthetics; - methane, isophorone diamine, xylylenediamine, hexahydroxylylene diamine, p- and m-aminobenzylamine, etc.). Dimethylamine, diethylamine or dipropylamine are preferably used to synthesize the Mannich intermediate. Example 1. a) Synthesis of Mannich intermediate base. To a 500-ml four-necked round-bottomed flask equipped with a mechanical stirrer, reflux condenser, thermometer and addition funnel, 94.1 g (1 mol) of phenol was charged and 136.4 g of a 33% aqueous solution of dimethylamine containing 1 mol was gradually added. pure dimethylamine. At the same time, the reaction mass is heated to 42 C. The stirrer is turned on and the mixture is stirred until the phenol is completely dissolved, while cooling to 20 ° C. To the resulting solution, 90.4 g of a 36.5% solution of formaldehyde in water containing 1.1 moles of bgo bases are added dropwise. substances. The rate of addition of formalin is regulated in such a way that the temperature of the reaction mass does not exceed 40 ° C. Upon completion of the addition of formalin, the reaction mass is heated to 90 ° C and at this temperature 1.17 g of potassium hydroxide is introduced in the form of a 10% aqueous solution. The contents of the flask are heated to boiling (EZ-SOO C) and boiled for 2 hours. 46.5 ml of toluene are added to the hot reaction mass, heated to froth and boiled for 30 minutes. The hot mixture is transferred to a separating funnel, stratified and the toluene layer is separated, and the extraction is repeated with the aqueous layer. The toluene extracts are combined, the toluene and volatile products are distilled off at atmospheric pressure, then under vacuum at an exact pressure of 10–20 mm Hg. to a mass temperature of 105 IO ° C. Obtain 142 g (93.2% of theoretical) of the product, characterized by the following indicators: Outward appearance - a transparent liquid of yellow-brown color. Content of titratable nitrogen,%: Found 9.37 Calculated for 2- (dimeshminaminomethyl) -phenol of the formula CjH, No.9.27 Viscosity at 25 ° С, mPa - from 48 Content of free phenol,% 4.7. b) Preparation of the desired 2- (diethylenetriaminomethyl) -phenol. In a 500 ml four-necked flask equipped with a mechanical stirrer, an addition funnel, a thermometer and an effective reflux condenser, connected through a venting tube to a Drexel absorber filled with water, 96 g of diethylene triamine are charged and heated to IOs. With stirring, 142 g of the synthesized intermediate base Mannich (molar ratio of the components 1: 1) are gradually introduced into the heated amine. The reaction mass is held at 120-130 ° C for 6-8 hours, and then for 1-2 hours at 130-1 ° C to complete the process. The reaction is controlled by weighing the flask with the reaction mass or determining the refractive index of the reaction mixture, which increases as dimethylamine increases and reaches a constant value in the range of 1,555-1,559. The mixture is cooled to 6070 ° C and poured into prepared containers. 194.8 g (99.1% of theoretical) of the product are obtained, characterized by the following indicators: Appearance - transparent, resinous yellow-brown pump, Content of titrated nitrogen,%: Found 19.58, Calculated for 2- (diethylenetriamino .methyl -phenol of the formula C H N O 20.09; Viscosity at, 937; Content of free phenol,% 3.5. Example 2. Under the conditions of Example 1a, from 94.1 g (1 mol) of phenol, 94.5 g (1.15 mol) of 36.5% aqueous formalin and 136.4 g of a 33% aqueous solution of dimethylamine (1 mol dimethylamine) get 146.2 g (95.3%

.of theoretical) product, characterized by the following indicators:.,

Appearance - transparent liquid of yellow-brown color,

Content of titrated nitrogen,%:

Found 9.25

Calculated 9.27

Viscosity at 135 mPa-s

The content of free phenol,% 3,6

Under the conditions of example 16, out of 146.2 g of synthesized 2- (dimethylaminomethyl) phenol and 99.6 diethylenetriamine (molar ratio 1: 1), 200.3 g (99.0% of theoretical) of the product are obtained, characterized by the following parameters:

Appearance - transparent resinous mass of yellow-brown color

Content of titrated nitrogen, 7 ,:

Found 19.25

Calculated for 2- (diethyl1-triaminomethyl) -phenol 20.09

Viscosity at 50 ° C, mPa-s 1350

The content of free phenol,% 2,

RIM EP 3. Under the conditions of example 1a, from 94.1 g (1 mol) of phenol, 98.6 g of 36.5% -horo formally 11a (1.2 mol of formaldehyde), 13.6, .4 g of 33% aqueous of dimethylamine solution (1 mol of the basic substance), 148.4 g (96.7% of the theoretical) of the product are obtained, characterized by the following indicators:

Appearance - a clear, yellowish-brown liquid.

Content of titrated nitrogen,%:

Found 8.95

Calculated for 2- (dimeshminaminometip) -phenol 9,27

Viscosity at, mPa with 303.

Content of free phenol,% 2.6.

Under the conditions of example 16, out of 148.4 g of the synthesized intermediate base of manniche and 5.0 g of ethylenediamine (molar ratio 1: 1), 160.0 g (98.0% of the theoretical) of the product are obtained with the following results:

Appearance - transparent resinous product of yellow color.

Content of titrated nitrogen%:

Found 16.28.

Calculated for 2- (ztilenediaminenomethyl) -phenol of the formula CgH;, N 16,85

Viscosity at, mPa-s 978

Free phenol content

%} with Z, E

Example 4. Under the conditions of example 1a, from 94.1 g (1 mol) of phenol, 102.2 g of 36.5% formalin (1.25 mol of formaldehyde) and 136.4 g of a 33% aqueous solution of dimethylamine ( 1 mol of the basic substance) receive 149.1 g (96.9% of theoretical) of a product having the following characteristics:

Appearance - transparent liquid of yellow-brown color.

Content of titrated nitrogen,%:

Found 8.92

Calculated 9.27

Viscosity at 25 ° C, mPa = 615

The content of free phenol,% 1,8

Under the conditions of Example 16, 161.6 g (98.5% of theory) of the productj having the following characteristics were obtained from 149.1 g of the obtained intermediate Mannich base and 59.3 g of etipenediamine (molar ratio 1: 1) :.

Appearance - transparent resinous mass of dark yellow color.

Content titrated azbt,%:

Found 16.23

Calculated for 2- (ethylenediaminemethyl) -phenol 16.85

Viscosity at mPa-s 1025

The content of free phenol,% 1,7

Example 5 a) Synthesis of the Mannich intermediate base. Under the conditions of Example 1a, from 94.1 (1 mol) phenol, 90.4 g of 36j5% -Horo formalin (1.1 mol of formaldehyde) and 73.1 g (1 mol) of diethpamine, receive 171.2 g (94.9 % of theoretical) product with the following indicators:

Appearance - transparent yellow-brown color,

Content of titrated nitrogen,%:

Found 7.53

Compounds for 2- (diethylaminomethyl-feiol of the formula C H ,, N0 7.81

Viscosity at 25 ° C, mPa-c 175

The content of free phenol,% 4,8

b) Synthesis of the desired 2- (triethylentetraminomethyl) -phenol. A four-pound flask with a capacity of 500 mp, equipped with a mechanical stirrer, an addition funnel, a thermometer and a direct condenser connected to condensate collection 7, was charged with 138.6 g of triethylene tetramine, heated before and with stirring, 171.2 g of 2- synthesized 2- ) -phenol. The reaction mass is held at 120 ° C for 4-5 hours, and then at 130–140 ° C - 1-1.5 hours. The process is monitored by the amount of diethylamine released. The result is 239.6 g (99.6% of theoretical) of a product that has the following characteristics: Appearance - a brown, transparent, resinous mass. Content of titrated nitrogen,%: Found 21.95. Vmisleno for 2- (triethi1nomers of nomethyl) -phenol of formula 22.22 Viscosity at 50 ° C, mPa "s 1A77 Content of free phenol, Example 6. Under the conditions of example 5a, from 94.1 g (1 mol) of phenol, 94.5 g of 36.5% formalin (1.15 mol of formaldehyde) and 73.1 g (1 mol of diethylamine get 174.1 (96.2% of theoretical) product with the following indicators: Appearance - clear yellow-brown liquid colors. Content of titrated nitrogen,%: Found 7.49 Calculated 7.81 Viscosity at 25 ° C, mPa-s 228 Content of free phenol,% 3 q Under the conditions of example 56 out of 174.1 g of synthesized intermediate On the basis of Mannich and 181.8 g of tetraethenpen pentamine (molar ratio 1: 1), 283.9 g (99.4% of theoretical) of the product are obtained, which characterizes with the following indicators: Appearance - a transparent dark expanded resinous mass. titrated nitrogen,%: Found 23.81 Calculated for 2- (tetraethylenepene aminomethyl) -phenol of the formula G., H 23.72 Viscosity at, mPa-s 1765 Content of free phenol,% 1.8 Example 7. Ll synthesis uses an intermediate the base of Man Nih, obtained in example 6a. Under the conditions of example 56, out of 179.3 g (1 mol) of the indicated intermediate 35 Mannich bases, 116.2 g (1 mol) of hexamethylenediamine, 220 g (99.0% of theoretical) of the product are obtained, which has the following characteristics: Appearance is transparent Brown mass. Titrated nitrogen content,%: Found 12.43 Calculated for 2- (hexamethylenediaminomethyl) -phenol of the formula 12.60 Viscosity at, mPaC 1561 Content of free phenol,% 2.9 and p and measure 8. Under the conditions of example 5a from 94.1 g (1 mol) of phenol, 90.4 g of 36.5% formalin (1.1 mol of formaldehyde) and 101 g (1 mol) of dipropylamine, 195.8 g (94.6% of the theoretical ) dipropylaminomethylphenol with the following indicators: Appearance - transparent brown liquid. Content of titratable nitrogen,%: Found 6.50 Calculated for 2- (dipropylaminomethane) -Fhairl of formula N0 6.76 Viscosity at 25 ° C, mPa-s 238 Content of free phenol,% 4.1 In conditions of example 56 of 195 , 8 g of the synthesized Mannich intermediate base and 128.6 g of the m-xylylenediamine (1: 1 molar ratio) give 226.8 g (99.1% of the theoretical) of the product, which is characterized by the following characteristics: Appearance - a transparent, resinous mass is dark Yellow Dve Content of titratable nitrogen,%: Found 11.38 Calculated for 2- (xylylenediaminomethyl) -phenol of the formula NjO 11.57 Viscosity at 50 ° C, mPa-s 2937 Content of free phenol,% 3.0 For m 9. For the synthesis the intermediate base of mannich obtained in example 1a. From 151.2 g of the indicated compound (1 mol) and 230.3 g (1 mol) of 4,4-diamino-dicyclohexylmethane, 314.9 g (99.5% of the theoretical) CLO product are obtained with the following indicators: Appearance is transparent gummy dark yellow mass. Titrated nitrogen content,%: Found 8.40 calculated for 2- (dicyclohexylme tandiaminometype) -phenol, formula CjoHjiN.O 8.85 Viscosity at 50 s, Sha-s 4588 Content of free phenol,% 3.1 Example 10. V the conditions of example 1a from 108.2 g (1 mol) o-cresol, 36.5% formalin (1.1 mol formaldehyde), 136.4 g of a 33% aqueous solution of di 1 methyl on 1 (1 mol of the basic substance) receive 156.3 g (94.6% of the theoretical) 2-methyl-4- (dimethylaminomethyl) phenol, characterized by the following indicators 14i :. Appearance - clear yellow-brown liquid. Content of titrated nitrogen,%: Found 8.09. Calculated for 2-methyl-4- (dimethyl aminomethyl) -phenol of formula C ,. H, .NO 8.47 Viscosity at, mPa-c 76 Content of free cresol,% 2.5. From 156.3 g of the synthesized Mannich intermediate base and 115.5 p-aminobenzylamine, under conditions of example 16, 227 are obtained. , 0 g (99.0% of the theoretical) product with the following indicators: Appearance - a transparent, yellow-colored, resinous product, Content of titrated nitrogen,%: Found 11.88 Calculated: D-2-methyl-4 (p-benzyl e ndiami nomethyl-phenyl of formula 11.56 Viscosity at 50 ° C, mPa-c 2069 Content of free cresol,% 1.8 Example 11. Under conditions of example 1a, from 220.3 g (1 mol) p-nonylphenol, 90, 4 g 36.5% formalindehyde (1.1 mol of formaldehyde), 136.4 g of a 33% solution of dimethylamine (1 mol of dimethylamine) give 261.0 g (93.8% of Theoretical) 2- (dimethylaminomethyl) -4-nonylphenol, which is characterized by indicators: Appearance - viscous dark brown liquid. Titrated nitrogen content,%: Found 5.21 Calculated for compound of formula C ,, Hj, NO 5.02 Viscosity at 25 ° C, mPa-s 946 Under the conditions of Example 16, of 261.0 g of the synthesized intermediate Mannich base and 122.7 g dipropylenetriamine (molar ratio of components 1: 1) get 357.7 g (99.6% of theoretical) of the product with the following indicators: Appearance -. transparent resinous mass of dark brown color. Content of titrated nitrogen,%: Found 11.06 Calculated dL of compounds of formula -, 11.57. Viscosity 3 (1 s, mPa "s 4966 All synthesized compounds were easily combined with liquid epoxy resins in the cold or with heating up to 30-40 ° C. From the above examples, it is clear that the process of obtaining polyaminoalkylphenols in stage 2 provides the target products with high yield and stabile indicators of quality (the content of free phenol is not more than 5%).

Claims (1)

METHOD FOR PRODUCING POLYAMINOalkylphenols by condensation of phenol with formaldehyde and amines, characterized in that, in order to increase the yield of the target product and improve its quality, phenol with formaldehyde and diapkylamine is first condensed at a molar ratio of 1: (1.10-1.25 ): 1, respectively, the resulting Mannich base is isolated and subjected to transamination with di- or polyamine.