SU1126597A1 - Process for preparing tall oil esters - Google Patents

Abstract

1. THE METHOD FOR OBTAINING COMPLEX ETHERS OF HEAT OIL by direct esterification is also distinguished by the fact that, in order to simplify and speed up the process, 4–8% of tall oil ester and anolamine trizt are introduced into the feedstock before the start of esterification. 2. The method according to Claim 1, which differs from that, the esterification is carried out at 180-200s for 3.5-5 hours.

Description

This invention relates to a technology for producing tall oil esters that can be used in the chemical industry in the production of varnishes, lubricating oils, softeners, and also for processing into polyurethane foams.

As is known, tall oil is a by-product of sulphate-pulp production and is a mixture of fatty resin acids and neutral substances, and is used in various industries.

A known method for producing tall oil complex and dialkanolamine esters by esterification at 130-140 ° C and under reduced pressure for 20 hours ij.

The closest to the proposed technical essence and the achieved result is a method of obtaining complex oils of tall oil and alcohols by esterification in the presence of a catalyst, followed by purification of the target product. Tin chloride or zinc dust mixed with zinc oxide is used as a catalyst

However, the use of a catalyst complicates the process because of the need to purify the target product, and also increases the cost of production.

The purpose of the invention is to simplify and accelerate the way

The goal is achieved according to the method of obtaining complex: e4 "tars of tall oil by direct esterification, before starting the esterification, and A-8% of ester tallow oil and triethanolamine are introduced into the raw materials. While the esterification is carried out at 180-200 C s for 3.5-5 h,

By reducing the amount of the added additive to less than 4%, the rate of the esterification process remains almost unchanged and the required acid number is reached in the same time as in the case without the use of any catalysts. For example, with the introduction of an additive in the amount of 3%, an acid number of 5 mg KOH / g is achieved in 12 hours. An increase in the amount of more than 8% is impractical because of the marked increase in the rate of the sterication process

not observed. For example, by adding tall oil ester and trizthanololamine in an amount of -. 9 or 10% process time

almost unchanged (3.5-5 hours). It can be assumed that the introduction of the target product contributes to the transesterification of the resulting esters of fatty acids and triethanolamine

resin acids according to the following scheme:

I stage. The formation of fatty acid ester

RCOOH + HOCHgCHjNlCHgCH OH) - RCOOCH CHaNlcHgCHeOH),

where R is the fatty acid radical.

Stage Transesterification with resins

Ksfsn5, sn2M (, sn2SNgOn1g

1 1 UNSA

RcOOCHjCMjN (cHjCH20H) - RCOOH

where R is the radical of resin acid. The technology of the method is

next

Tall oil ,, triethanol and a calculated amount (4–8%) previously obtained by any known reactor is loaded into a standard reactor equipped with a cooler, a mechanical stirrer and a collection of reactive water.

the tall ester method

oils and triethanolamine. The reaction mixture is gradually heated at

this stirring and maintained at 180–200 ° C for up to 3.5–5 h until the required acid number is obtained — no more than 5 mg KOH / g. The resulting ester is discharged from the reactor

and used without further purification.

The percentage of free hydroxyl groups in the resulting product can be adjusted by

changes in the ratio of the starting components.

Example: A 0.57 liter three-necked flask equipped with a mechanical stirrer, a Würz nozzle, a condenser and a reaction water receiver was charged with 110 g of tall oil (TM), 90 g of triethanolamine TEOA) and 8 g of TM and TEOA ester 4% of the total weight and heated in a silicone bath to 180 ° C. To prevent foaming of the reaction mixture, 0.002 g 0.001% of polymethylsiloxane (PMS-200T or other surfactant surfactant) is added. Mixing speed 240 rpm. Esterification is carried out for 4. h until reaching an acid number of not more than 5 mg KOH / H. The yield of the target product is 98%. The resulting product is a viscous homogeneous opaque liquid of dark brown color, the viscosity relative to the VZ-1 viscometer at 2040.5 V 120 s, with a content of free hydroxyl groups of 14%. Example 2. The process is carried out in the same apparatus and with the same ratios of the starting reagents as in Example 1, with the only difference that the synthesis is carried out at 190 ° C and 6% ester W and TEOA Cl2 g are added ). Esterification is practically completed within 3.5 hours. The product yield is 98%, q. 4.3.8 mg KOH / g, and the OH group content is 14.1%. EXAMPLE 3 The process is carried out in a similar apparatus as in Example 1, with 8% ester-Cl6 g) TM and TEOA added at the start of the reaction and with. Esterification practically ends within 4 hours, k.ch. 3.5, the content of OH groups is 13.9%. Thus, the use of the proposed method allows obtaining the target product in a single process} reducing the duration of the process, excluding the target product from the technical purification process. In addition, the resulting esters are a valuable raw material in the preparation of polyurethane foams (P1U), since the use of toxic and expensive amine catalysts is excluded in the compositions for the preparation of P1Us with the participation of esters prepared by this method.

Claims (2)

1. METHOD FOR PRODUCING COMPLEX ETHERS OF TALL OIL by direct esterification, do I distinguish with what _? that, in order to simplify and accelerate the method, before starting the esterification, 4-8% of tall oil ester and triethanolamine are introduced into the feedstock. 2. The method according to π.1, with the fact that the esterification is carried out at 180-200 ° C for 3.5-5 hours. Joint venture M 126597 ϊ not observed. So, for example, when adding tall oil ester and triethanolamine in an amount of - ·. 9 or 10%, the duration of the process 5 remained almost unchanged (3.5-5 hours). It can be assumed that the introduction of the target product promotes the transesterification of the formed esters of fatty acids and triethanolamine with resin acids according to the following scheme: 1st stage. Fatty acid ester formation RCOOH + HOCH ₂ CH _r x _(r CH CH he _r \ - - * "COOCH ₂ CH _gm (CH _z CH _z OH) _2; wherein R - fatty acid radical. P stage. Transesterification with resin acids ysfsn _{ , sn _g n (sn _g sn _g he) _g ChsoN . I _ ^ cN ya'soosn _{g g} m _(r CH CH he _{g) a} * RCOOW wherein R ¹ - a radical of a resin acid. The technology of the method is as follows. ' Tall oil, triethanolamine and the calculated amount (4-8%) of tall oil ester and triethanolamine previously obtained by any known method are charged into a standard reactor equipped with a refrigerator, a mechanical stirrer and a reaction water collector. The reaction mixture is gradually heated with constant stirring and kept at 180-200 ° C for up to 3.5-5 hours to obtain the required acid number of not more than 5 mg KOH / g. The resulting ether is discharged from the reactor and used without further purification. The percentage of free hydroxyl groups in the resulting product can be controlled by changing the ratio of the starting components. Example 1. In a 0.5-liter three-necked flask equipped with a mechanical stirrer, a Wurz nozzle with a refrigerator and a reaction water receiver, 110 g of tall oil (TM), 90 g of triethanolamine (TEoA) and 8 g of TM t 1 ester are charged